Fluorocarbon chain modified cobalt nickel-aluminum hydrotalcite as well as preparation method and application thereof

Abstract

The invention relates to fluorocarbon chain modified cobalt nickel-aluminum hydrotalcite and a preparation method and application thereof, ions in the cobalt nickel-aluminum hydrotalcite are Co < 2 + >, Ni < 2 + > and Al < 3 + > respectively, and a fluorocarbon chain is prepared from at least one compound in formulas (I)-(III); comprising the following steps: S1, stirring and mixing a Co < 2 + > aqueous solution, a Ni < 2 + > aqueous solution, an Al < 3 + > aqueous solution and a urea aqueous solution in an inert gas atmosphere, then carrying out a hydrothermal reaction, and after the reaction is finished, carrying out post-treatment to obtain cobalt nickel-aluminum hydrotalcite; and S2, dispersing the cobalt nickel-aluminum hydrotalcite in anhydrous toluene, reacting the cobalt nickel-aluminum hydrotalcite with at least one compound in formulas (I)-(III) under the action of triethylamine in an inert gas atmosphere, and after the reaction is finished, performing post-treatment to obtain fluorocarbon chain modified cobalt nickel-aluminum hydrotalcite, the hydrotalcite is applied to preparation of naphthenic alcohol and naphthenic ketone by catalyzing partial oxidation of naphthenic hydrocarbon. The method has the advantages of high selectivity, high product yield, low content of naphthenic hydroperoxide in the reaction process, and high operation safety.

Description

Technical Field

[0001] This invention relates to the technical field of catalysts, and in particular to a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite, its preparation method, and its application. Background Technology

[0002] Catalytic oxidation of cycloalkanes is a major method for directly converting hydrocarbons widely found in fossil resources into high-value-added alcohols and ketones, and it has wide applications in the chemical industry (CN202111006432.X; CN202010884408.5; CN201911161924.9), especially when molecular oxygen is used as the oxidant. However, because the chemical reactivity of the partially oxidized products (cycloalkyl alcohols and cycloalkyl ketones) is higher than that of the substrate cycloalkanes, these partially oxidized products are prone to deep oxidation, generating ring-opening products such as aliphatic diacids and their derivatives. This not only reduces the selectivity of the partially oxidized products but also increases the energy consumption and equipment requirements for separation and purification, which is not conducive to industrial production (Chemical Engineering Journal, 2022, 443: 136126; Chemical Engineering Science, 2022, 260: 117825; Molecular Catalysis, 2023, 535: 112853). The root causes of the deep oxidation of cycloalkanes by partial oxidation products are mainly: (1) the high reactivity of the partial oxidation products (cycloalkyl alcohols and cycloalkyl ketones); (2) the oxidation of CH bonds by O2 is a free radical diffusion process, and the partial oxidation products are easily attacked by non-diffusion free radicals and thus undergo deep transformation; (3) the partial oxidation products are easily and frequently contacted with the catalytic active center, resulting in deep catalytic oxidation transformation.

[0003] In the current chemical industry, the catalysts used for the catalytic oxidation of cycloalkanes are mainly salts, complexes, and derivatives of cobalt(II) and manganese(II). These catalysts can catalyze the oxidation of cycloalkanes by O2 to partially oxidized products such as alcohols and ketones (CH bonds), and also catalyze the oxidation of alcohols and ketones by O2 to deeply oxidized products. Therefore, effectively avoiding frequent contact between partially oxidized products (cycloalkyl alcohols and cycloalkyl ketones) and the catalytically active sites will help prevent the deep oxidation of alcohols and ketones during the partial oxidation of cycloalkanes, achieving efficient and selective oxidation of cycloalkanes to partially oxidized products such as cycloalkyl alcohols and cycloalkyl ketones. This is also of great significance for reducing the difficulty and equipment requirements for the separation and purification of partially oxidized cycloalkanes in industry, reducing separation energy consumption, achieving safe production of cycloalkanes, and saving energy and reducing emissions.

[0004] Hydrotalcite is a layered material formed by the interaction of positive and negative ions. It not only contains abundant metal active sites, serving as catalytic active centers, but also exhibits a degree of tunable catalytic performance. Its layered structure also provides a degree of confinement, inhibiting the disordered diffusion of species. Furthermore, the CF bond, due to its low polarity, exhibits strong repulsion towards some oil compounds, especially some highly polar organic compounds, demonstrating strong oleophobicity (CN115926069A; WO2022059620A1). The partial oxidation of cycloalkanes to cycloalkyl alcohols and cycloalkyl ketones is a process that increases polarity. Therefore, using hydrotalcite modified with CF bonds as a catalyst for the O2-catalyzed oxidation of cycloalkanes not only suppresses the disordered diffusion of free radicals during oxidation through its layered structure, preventing some oxidation products from being deeply oxidized by free radical attack, but the CF bonds also promote the detachment of highly polar cycloalkyl alcohols and cycloalkyl ketones from the catalytic active center and prevent their disordered diffusion process from contacting the catalytic active center, thus preventing their deep oxidation. This achieves efficient and selective oxidation of cycloalkanes to cycloalkyl alcohols and cycloalkyl ketones. Therefore, using CF-modified hydrotalcite as a catalyst for the partial oxidation of cycloalkanes will be beneficial for achieving efficient and selective catalytic oxidation of cycloalkanes to cycloalkyl alcohols and cycloalkyl ketones, which is of great significance for the safe, energy-saving, and emission-reducing production of cycloalkanes in industry. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the first objective of this invention is to provide a cobalt-nickel-aluminum layered double hydroxide (LDH) modified with a fluorocarbon chain. This LDH is modified with a fluoroalkylsilane as a modifying group to construct a confined relay catalyst with interfacial contact control properties. This catalyst is then applied to the O2-catalyzed partial oxidation of cycloalkanes. The layered structure of the LDH creates a confined catalytic environment, limiting the disordered diffusion of free radicals during the O2 oxidation of cycloalkanes and preventing the partial oxidation products from being attacked by free radicals and undergoing deep oxidation. The cobalt-nickel bimetallic structure forms relay catalytic sites, catalyzing the conversion of intermediate peroxides generated during the cycloalkanes oxidation process and utilizing their oxidizing properties to achieve efficient and stable oxidation of cycloalkanes. The fluorocarbon chain forms an interfacial contact control factor, promoting the detachment of cycloalkyl alcohols and cycloalkyl ketones, which are more polar than cycloalkanes, from the catalytic interface and preventing contact between cycloalkyl alcohols and cycloalkyl ketones and the catalytic center, thus preventing the deep oxidation of the partial oxidation products.

[0006] The second objective of this invention is to provide a method for preparing cobalt-nickel-aluminum hydrotalcite modified with fluorocarbon chains, which has the advantages of simple preparation and high yield.

[0007] The third objective of this invention is to provide an application of fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite, which uses fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite as a catalyst. This triple approach synergistically promotes the efficient and selective partial oxidation of cycloalkanes by O2, resulting in high selectivity and high product yield. Furthermore, the reaction process involves low cycloalkyl hydroperoxide content and high operational safety, making it an efficient, feasible, and safe route for the synthesis of cycloalkyl alcohols and cycloalkyl ketones.

[0008] To achieve the first objective mentioned above, the present invention provides the following technical solution:

[0009] A cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, wherein the cobalt-nickel-aluminum hydrotalcite contains Co ions as follows: 2+ Ni 2+ And Al 3+ The fluorocarbon chain is made of at least one compound of formula (I) to (III);

[0010] ;

[0011] Among them, the Each is independently selected from C1 to C6 alkoxy groups.

[0012] Furthermore, the fluorocarbon chain is made of at least one compound of formulas (IV) to (IX);

[0013] .

[0014] To achieve the second objective mentioned above, the present invention provides the following technical solution:

[0015] A method for preparing a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite includes the following steps:

[0016] S1 first Co 2+ Aqueous solution, Ni 2+ Aqueous solution, Al 3+ The aqueous solution and the urea aqueous solution were stirred and mixed under an inert gas atmosphere, and then subjected to a hydrothermal reaction. After the reaction was completed, the cobalt-nickel-aluminum hydrotalcite was obtained through post-treatment.

[0017] S2 first disperses the cobalt-nickel-aluminum hydrotalcite obtained in S1 in anhydrous toluene, and then reacts it with at least one of the compounds in formulas (I) to (III) in an inert gas atmosphere under the action of triethylamine. After the reaction is completed, the cobalt-nickel-aluminum hydrotalcite modified with fluorocarbon chain is obtained.

[0018] Furthermore, in S1, Co is controlled 2+ The concentration of the aqueous solution is 0.01~10.00 mol / L, Ni 2+The concentration of the aqueous solution is 0.01~10.00 mol / L, Al 3+ The concentration of the aqueous solution is 0.01~10.00mol / L, and the concentration of the urea aqueous solution is 0.01~20.00mol / L.

[0019] Furthermore, in S1, Co is controlled 2+ The concentration of the aqueous solution is 0.10~1.00 mol / L, Ni 2+ The concentration of the aqueous solution is 0.10~1.00 mol / L, Al 3+ The concentration of the aqueous solution is 0.10~1.00mol / L, and the concentration of the urea aqueous solution is 0.10~1.00mol / L.

[0020] Furthermore, in S1, Co 2+ Ni 2+ The molar ratio is 1:(0.10~10.00), Co 2+ and Ni 2+ Al 3+ The molar ratio is 1:(0.01~100.00), Co 2+ and Ni 2+ And Al 3+ The molar ratio of urea is 1:(0.01~100.00).

[0021] Furthermore, in S1, Co 2+ Ni 2+ The molar ratio is 1:(0.10~10.00), Co 2+ and Ni 2+ Al 3+ The molar ratio is 1:(0.20~0.50), Co 2+ and Ni 2+ And Al 3+ The molar ratio of urea is 1:(0.10~10.00).

[0022] Furthermore, in S1, the reaction temperature is controlled at 100~200℃ and the reaction time is controlled at 8~72h.

[0023] Furthermore, in S1, the reaction temperature is controlled at 120~180℃ and the reaction time is controlled at 12~36h.

[0024] Furthermore, in S1, after the reaction is completed, the reactants are sequentially centrifuged and washed with deionized water.

[0025] Further, in S2, the ratio of cobalt-nickel-aluminum hydrotalcite, at least one compound of formula (I) to (III) above, anhydrous toluene, and triethylamine is controlled to be 1g: (0.0001~1.0000)mol: (10~200)mL: (0.01~10.00)g.

[0026] Furthermore, in S2, the ratio of cobalt-nickel-aluminum hydrotalcite, at least one compound of formula (I) to (III) above, anhydrous toluene, and triethylamine is controlled to be 1g: (0.0010~0.1000)mol: (50~100)mL: (1.00~5.00)g.

[0027] Furthermore, in S2, the reaction temperature is controlled at 30~120℃ and the reaction time is controlled at 6~96h.

[0028] Furthermore, in S2, the reaction temperature is controlled at 80~100℃ and the reaction time is 12~24h.

[0029] Furthermore, in S2, after the reaction is completed, the reactants are sequentially subjected to vacuum filtration, washing with ethanol, washing with water, and vacuum drying at 70~90℃.

[0030] To achieve the third objective mentioned above, the present invention provides the following technical solution:

[0031] Application of a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones.

[0032] Furthermore, the specific implementation method for the partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones is as follows: after dispersing cobalt-nickel-aluminum hydrotalcite modified with fluorocarbon chains in cycloalkanes, stirring and heating the mixture in a sealed reaction system while introducing oxygen, stirring and reacting, and after post-processing, obtaining a reaction mixture containing partially oxidized products cycloalkyl alcohols and cycloalkyl ketones.

[0033] Furthermore, in the reaction process, the cycloalkane is cyclopentane, cyclohexane, cycloheptane, cyclooctane, or cyclododecane, and the ratio of the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite to the cycloalkane is controlled to be 1 mg: (1~1000) mmol.

[0034] Furthermore, during the reaction, the ratio of fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite to cycloalkanes is controlled to be 1 mg: (10~100) mmol.

[0035] Furthermore, during the reaction process, the stirring temperature is controlled to be 80~160℃, the reaction pressure is 0.50~1.50MPa, and the reaction time is 6~24h.

[0036] Furthermore, during the reaction process, the stirring temperature is controlled to be 100~150℃, the reaction pressure is 0.80~1.00MPa, and the reaction time is 8~15h.

[0037] In summary, the beneficial technical effects of the present invention are as follows:

[0038] 1. The carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite of the present invention constructs a confined relay catalyst with interfacial contact control performance. The layered structure of the hydrotalcite creates a confined catalytic environment, limiting the disordered diffusion of free radicals during the O2 oxidation of cycloalkanes and preventing some oxidation products from being attacked by free radicals and undergoing deep oxidation transformation. The cobalt-nickel bimetallic structure forms relay catalytic sites, catalyzing the transformation of intermediate peroxides generated during the cycloalkanes oxidation process and utilizing their oxidizing properties to achieve efficient and stable oxidation transformation of cycloalkanes. The carbon-fluorine chain forms interfacial contact control factors, promoting the detachment of cycloalkyl alcohols and cycloalkyl ketones, which are more polar than cycloalkanes, from the catalytic interface and preventing contact between cycloalkyl alcohols and cycloalkyl ketones and the catalytic center, thus preventing the deep oxidation transformation of some oxidation products. These three mechanisms synergistically promote the efficient and selective partial oxidation of cycloalkanes by O2.

[0039] 2. The present invention relates to a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite-catalyzed partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. This method for partial oxidation of cycloalkanes not only boasts high conversion and high selectivity for the partially oxidized products, but also exhibits low residual cycloalkyl hydroperoxide content, good operational safety, and the ability to significantly suppress common industrial side reactions (such as deep oxidation to aliphatic diacids). It provides a new technical route for the efficient synthesis of cycloalkane partial oxidation products. This invention not only has significant industrial application prospects and theoretical research value, but also provides valuable insights for improving the selectivity of other catalytic oxidation systems.

[0040] 3. This invention utilizes a cobalt-nickel-aluminum layered double hydroxide modified with a fluorocarbon chain as an interfacial contact-controlled relay catalyst for the O2-catalyzed oxidation of cycloalkanes. The novel and ingenious structural design results in high catalytic efficiency, structural stability, and ease of industrial application. In the O2 oxidation of cycloalkanes, the substrate conversion rate is high, the selectivity for cycloalkyl alcohols and cycloalkyl ketones is high, and the over-oxidation of some oxidation products is effectively suppressed, significantly reducing the formation of aliphatic diacids and their derivatives. The low selectivity for byproducts not only reduces the energy consumption for product separation but also facilitates continuous operation of the reaction system. This method is expected to solve the common problem of easy over-oxidation of products to form diacids and other byproducts during the industrial catalytic oxidation of cycloalkanes, achieving efficient and stable synthesis of some oxidation products. It possesses both good industrial application value and scientific research reference significance, representing a new strategy for the efficient, feasible, and highly selective catalytic oxidation of cycloalkanes. Attached Figure Description

[0041] Figure 1These are XDR images of the cobalt-nickel-aluminum hydrotalcite prepared in Example 2 of this invention and the carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite prepared in Example 21.

[0042] Figure 2 These are FT-IR images of the cobalt-nickel-aluminum hydrotalcite prepared in Example 2 of this invention and the carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite prepared in Example 21.

[0043] Figure 3 This is a gas chromatogram of the cycloalkyl alcohol and cycloalkyl ketone standard samples of the present invention.

[0044] Figure 4 This is a gas chromatogram of the oxidation product obtained in Example 42 of the present invention. Detailed Implementation

[0045] To make the technical means, creative features, objectives and effects of this invention clearer and easier to understand, the invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0046] Example 1: A cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention, wherein the cobalt-nickel-aluminum hydrotalcite contains Co ions. 2+ Ni 2+ And Al 3+ The fluorocarbon chain is made of at least one compound of formula (I) to (III);

[0047] ;

[0048] Among them, the Each is independently selected from C1 to C6 alkoxy groups.

[0049] In this embodiment, the fluorocarbon chain is preferably made of at least one compound of formulas (IV) to (IX);

[0050] .

[0051] The naming rules for cobalt-nickel-aluminum hydrotalcite are as follows: LDH-Co 0.1 & 20 Ni 0.2 & 20 Al 0.6 & 20 AT 0.8 & 30 @150@24 , indicating that during the preparation process, Co 2+ The concentration of the aqueous solution is 0.1 mol / L, and the volume used is 20 mL; Ni 2+ The concentration of the aqueous solution is 0.2 mol / L, and the volume used is 20 mL; Al 3+ The concentration of the aqueous solution was 0.6 mol / L, and the volume used was 20 mL; the concentration of the urea aqueous solution was 0.8 mol / L, and the volume used was 30 mL; the hydrothermal reaction was carried out at 150℃ for 24 h.

[0052] The naming convention for carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcites is as follows: LDH-Co 0.1& 20 Ni 0.2 & 20 Al 0.6 & 20 U 0.8 & 30 @150@24-F(V)@0.001@110@0.5@100@24 indicates that during the preparation process, Co 2+ The concentration of the aqueous solution is 0.1 mol / L, and the volume used is 20 mL; Ni 2+ The concentration of the aqueous solution is 0.2 mol / L, and the volume used is 20 mL; Al 3+ The concentration of the aqueous solution was 0.6 mol / L, and the volume used was 20 mL; the concentration of the urea aqueous solution was 0.8 mol / L, and the volume used was 30 mL; the hydrothermal reaction was carried out at 150℃ for 24 h. In the fluorocarbon chain modification process, the fluorosilane structure was shown in formula (V). The mass ratio of cobalt-nickel-aluminum hydrotalcite (g) to the moles of fluorosilane (mol) was 1:0.001; the mass ratio of cobalt-nickel-aluminum hydrotalcite (g) to the volume of anhydrous toluene (mL) was 1:110; the mass ratio of cobalt-nickel-aluminum hydrotalcite to triethylamine was 1:0.5; the reaction temperature of the cobalt-nickel-aluminum hydrotalcite with the fluorosilane was 100℃; and the reaction time was 24 h.

[0053] This invention also discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with fluorocarbon chains, comprising the following steps:

[0054] S1 first Co 2+ Aqueous solution, Ni 2+ Aqueous solution, Al 3+ The aqueous solution and the urea aqueous solution were stirred and mixed under an inert gas atmosphere, and then subjected to a hydrothermal reaction. After the reaction was completed, the cobalt-nickel-aluminum hydrotalcite was obtained through post-treatment.

[0055] S2 first disperses the cobalt-nickel-aluminum hydrotalcite obtained in S1 in anhydrous toluene, and then reacts it with at least one of the compounds in formulas (I) to (III) in the presence of triethylamine in an inert gas atmosphere. After the reaction is completed, the cobalt-nickel-aluminum hydrotalcite modified with fluorocarbon chain is obtained through post-treatment.

[0056] Example 2: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in S1, 0.15 mol / L of Co... 2+ 20 mL of aqueous solution, 0.15 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+20 mL of an aqueous solution and 20 mL of a 0.8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2, 0.7567g.

[0057] Example 3: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in step S1, 0.15 mol / L of Co... 2+ 20 mL of aqueous solution, 0.15 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of a 0.8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 100 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @100@1 2, 0.7437g.

[0058] Example 4: This is a method for preparing a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in S1, 0.15 mol / L of Co... 2+ 20 mL of aqueous solution, 0.15 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of a 0.8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 180 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @180@1 2, 0.7367g.

[0059] Example 5: This is a method for preparing a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in S1, 0.15 mol / L of Co... 2+ 20 mL of aqueous solution, 0.15 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+20 mL of an aqueous solution and 20 mL of a 0.8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2, 0.7324g.

[0060] Example 6: This is a method for preparing a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in S1, 0.15 mol / L of Co... 2+ 20 mL of aqueous solution, 0.15 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of a 0.8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 8 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@8 0.7165g.

[0061] Example 7: This is a method for preparing a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite disclosed in this invention. The difference from Example 1 is that, in S1, 0.15 mol / L of Co... 2+ 20 mL of aqueous solution, 0.15 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of a 0.8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 36 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@3 6, 0.7462g.

[0062] Example 8: This is a method for preparing a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in S1, 0.15 mol / L of Co... 2+ 20 mL of aqueous solution, 0.15 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+20 mL of an aqueous solution and 20 mL of a 0.8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 72 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@7 2, 0.7254g.

[0063] Example 9: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in S1, 3 mol / L of Co... 2+ 20 mL of aqueous solution, 0.03 mol / L Ni 2+ 20 mL of aqueous solution, 1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of an 8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by a hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co3& 20 Ni 0.03 & 20 Al1& 20 U8& 20 @120@1 2, 2.64g.

[0064] Example 10: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in S1, 3 mol / L of Co... 2+ 20 mL of aqueous solution, 0.3 mol / L Ni 2+ 20 mL of aqueous solution, 1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of a 9 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co3& 20 Ni 0.3 & 20 Al1& 20 U9& 20 @120@1 2, 3.75g.

[0065] Example 11: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 0.3 mol / L of Co... 2+ 20 mL of aqueous solution, 3 mol / L Ni 2+ 20 mL of aqueous solution, 1 mol / L Al 3+20 mL of an aqueous solution and 20 mL of a 9 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.3 & 20 Ni3& 20 Al1& 20 U8& 20 @120@1 2, 3.34g.

[0066] Example 12: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 0.03 mol / L of Co... 2+ 20 mL of aqueous solution, 3 mol / L Ni 2+ 20 mL of aqueous solution, 1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of an 8 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by a hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.03 & 20 Ni3& 20 Al1& 20 U8& 20 @120@1 2, 3.12g.

[0067] Example 13: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 1 mol / L of Co is added to a 100 mL hydrothermal reactor with a polytetrafluoroethylene inner liner. 2+ 20 mL of aqueous solution, 1 mol / L Ni 2+ 20 mL of aqueous solution, 0.01 mol / L Al 3+ 20 mL of aqueous solution and 20 mL of 4 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, and then hydrothermally reacted at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co1& 20 Ni1& 20 Al 0.01 & 20 U4& 20 @120@1 2, 3.45g.

[0068] Example 14: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 0.1 mol / L of Co... 2+ 20 mL of aqueous solution, 0.1 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+20 mL of an aqueous solution and 20 mL of a 0.6 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.1 & 20 Ni 0.1 & 20 Al 0.1 & 20 AT 0.6 & 20 @120@1 2, 0.6867g.

[0069] Example 15: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 0.5 mol / L of Co... 2+ 20 mL of aqueous solution, 0.5 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of a 2.2 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.5 & 20 Ni 0.5 & 20 Al 0.1 & 20 AT 2.2 & 20 @120@1 2, 0.8527g.

[0070] Example 16: This invention discloses a method for preparing a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 0.01 mol / L of Co is added to a 100 mL hydrothermal reactor with a polytetrafluoroethylene inner liner. 2+ 20 mL of aqueous solution, 0.01 mol / L Ni 2+ 20 mL of aqueous solution, 1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of a 0.3 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.01 & 20 Ni 0.01 & 20 Al1& 20 AT 0.3 & 20 @120@1 2, 0.2512g.

[0071] Example 17: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 1.5 mol / L of Co... 2+ 20 mL of aqueous solution, 1.5 mol / L Ni 2+ 20 mL of aqueous solution, 1 mol / L Al 3+20 mL of an aqueous solution and 20 mL of a 0.04 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 1.5 & 20 Ni1.5& 20 Al1& 20 AT 0.04 & 20 @120@1 2, 2.71g.

[0072] Example 18: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 1.5 mol / L of Co... 2+ 20 mL of aqueous solution, 1.5 mol / L Ni 2+ 20 mL of aqueous solution, 1 mol / L Al 3+ 20 mL of an aqueous solution and 20 mL of a 0.4 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, followed by hydrothermal reaction at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 1.5 & 20 Ni1.5& 20 Al1& 20 AT 0.4 & 20 @120@1 2, 3.24g.

[0073] Example 19: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 0.15 mol / L of Co... 2+ 20 mL of aqueous solution, 0.15 mol / L Ni 2+ 20 mL of aqueous solution, 0.1 mol / L Al 3+ 20 mL of aqueous solution and 20 mL of 4 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, and then hydrothermally reacted at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U4& 20 @120@1 2, 0.7264g.

[0074] Example 20: This invention discloses a method for preparing a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in S1, 0.015 mol / L of Co... 2+ 20 mL of aqueous solution, 0.015 mol / L Ni 2+ 20 mL of aqueous solution, 0.01 mol / L Al 3+20 mL of aqueous solution and 20 mL of 4 mol / L urea aqueous solution were mixed and stirred for 15 min under a N2 atmosphere, and then hydrothermally reacted at 120 °C for 12 h. After the reaction was completed, the solid was separated by centrifugation, washed with 3 × 10 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to obtain cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.015 & 20 Ni 0.015 & 20 Al 0.01 & 20 AT 0.8 & 20 @120@1 2, 0.1021g.

[0075] Example 21: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6,0.0824g.

[0076] Figure 1 These are the X-ray diffraction (XRD) spectra of the cobalt-nickel-aluminum hydrotalcite (Co&Ni-Al LDH) prepared in Example 2 of this invention, the carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite (F-Co&Ni-Al LDH) prepared in Example 21, the laboratory-prepared magnesium-aluminum hydrotalcite (Mg-Al LDH), and the standard magnesium-aluminum hydrotalcite (Mg-Al LDH). Figure 1 As can be seen, the crystal structures of the synthesized cobalt-nickel-aluminum hydrotalcite (Co&Ni-Al LDH), fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (F-Co&Ni-Al LDH), and magnesium-aluminum hydrotalcite (Mg-Al LDH) are consistent with those of the standard magnesium-aluminum hydrotalcite (Mg-Al LDH), indicating that the cobalt-nickel-aluminum hydrotalcite (Co&Ni-Al LDH) and fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (F-Co&Ni-Al LDH) prepared in Example 2 have correct structures and the materials were successfully prepared.

[0077] Figure 2 These are the Fourier transform infrared (FT-IR) spectra of the cobalt-nickel-aluminum hydrotalcite (Co&Ni-Al LDH) prepared in Example 2 and the carbon-fluorine chain-modified cobalt-nickel-aluminum hydrotalcite (F-Co&Ni-Al LDH) prepared in Example 21. Figure 2The infrared spectrum shows that the fluorocarbon chain modification largely maintains the infrared structure of cobalt-nickel-aluminum hydrotalcite (Co&Ni-Al LDH), indicating that the fluorocarbon chain modification process has little impact on the structure of Co&Ni-Al LDH. Figure 1 XRD analysis confirmed that the cobalt-nickel-aluminum hydrotalcite (Co&Ni-Al LDH) and the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (F-Co&Ni-Al LDH) prepared in Example 2 had correct structures and were successfully synthesized. Furthermore, compared to the FT-IR spectrum of cobalt-nickel-aluminum hydrotalcite (Co&Ni-Al LDH), the FT-IR spectrum of the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (F-Co&Ni-Al LDH) showed a higher spectral density at 1148 cm⁻¹. -1 An absorption peak appears at (), which is mainly a characteristic absorption peak of the CF bond, further indicating the successful introduction of the carbon-fluorine chain. Combined with the XRD results, it shows that the modification process did not destroy the main layered structure of the hydrotalcite. The carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite (F-Co&Ni-AlLDH) was successfully synthesized.

[0078] Table 1

[0079]

[0080] As shown in Table 1, the inductively coupled plasma (ICP) elemental analysis of the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (F-Co&Ni-AlLDH) prepared in Example 2 is shown in Table 1. The results show that the average content of aluminum in the material is 4.8695%, the average content of cobalt is 14.8759%, and the average content of nickel is 14.7538%. The three elements coexist relatively stably in the material, which to some extent indicates the successful synthesis of the material.

[0081] Example 22: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.47 g (0.001 mol) of fluorosilane (V) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅴ）@0.01@100@5@90@1 6,0.0828g.

[0082] Example 23: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.57 g (0.001 mol) of fluorosilane (VI) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅵ）@0.01@100@5@90@1 6,0.0836g.

[0083] Example 24: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.41 g (0.001 mol) of fluorosilane (VII) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅶ）@0.01@100@5@90@1 6,0.0826g.

[0084] Example 25: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.51 g (0.001 mol) of fluorosilane (VIII) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅷ）@0.01@100@5@90@16,0.0831g.

[0085] Example 26: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.61 g (0.001 mol) of fluorosilane (IX) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅸ）@0.01@100@5@90@1 6,0.0837g.

[0086] Example 27: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 4 mg (0.00001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅳ）@0.0001@100@5@90@1 6,0.0821g.

[0087] Example 28: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.037 g (0.0001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was completed, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅳ）@0.001@100@5@90@1 6,0.0820g.

[0088] Example 29: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 3.68 g (0.01 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was completed, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.1@100@5@90@1 6,0.81g.

[0089] Example 30: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 100mL three-necked round-bottom flask... LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 36.8 g (0.1 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise with stirring. After the addition was complete, the mixture was stirred and reacted at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was completed, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅳ）@1@100@5@90@1 6,0.0823g.

[0090] Example 31: This invention discloses a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. The difference from Example 1 is that, in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 21.00 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 3.68 g (0.01 mol) of fluorosilane (IV) and 5 g of triethylamine were added dropwise with stirring. After the addition was complete, the mixture was stirred and reacted at 90 °C for 16.0 h under a N2 atmosphere. After the reaction was completed, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain.LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.01@10@5@90@1 6,0.81g.

[0091] Example 32: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 20 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.01@200@5@90@1 6,0.0822g.

[0092] Example 33: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 250 mL three-necked round-bottom flask... LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 21.00 g of the mixture was suspended in 100 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 3.68 g (0.01 mol) of fluorosilane (IV) and 0.01 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@0.01@90@1 6,0.80g.

[0093] Example 34: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@120.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.1 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@1@90@1 6,0.0810g.

[0094] Example 35: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 1.0 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 90 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@10@90@1 6,0.0825g.

[0095] Example 36: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 30 °C under a N2 atmosphere for 16.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@5@30@1 6,0.0782g.

[0096] Example 37: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 80 °C for 16.0 h under a N2 atmosphere. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@5@80@1 6,0.0810g.

[0097] Example 38: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 120 °C for 16.0 h under a N2 atmosphere. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@5@120@1 6,0.0820g.

[0098] Example 39: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred at 90 °C under a N2 atmosphere for 6.0 h. After the reaction was complete, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@ 6,0.0801g.

[0099] Example 40: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 90 °C for 24.0 h under a N2 atmosphere. After the reaction was completed, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@2 4,0.0825g.

[0100] Example 41: This is a method for preparing cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, as disclosed in this invention. The difference from Example 1 is that, in step S2, the cobalt-nickel-aluminum hydrotalcite is placed in a 50mL three-necked round-bottom flask... LDH- Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 20.10 g of the mixture was suspended in 10 mL of anhydrous toluene and stirred at room temperature for 15 min. Simultaneously, 0.37 g (0.001 mol) of fluorosilane (IV) and 0.5 g of triethylamine were added dropwise. After the addition was complete, the mixture was stirred and reacted at 90 °C for 96.0 h under a N2 atmosphere. After the reaction was completed, the reactants were successively filtered under reduced pressure, washed with 3 × 10 mL of anhydrous ethanol, washed with 5 × 10 mL of water, and dried under vacuum at 80 °C for 8.0 h to obtain a cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 U 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@9 6,0.0816g.

[0101] Example 42: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 16.8%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 51%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0102] Figure 3 The image shows the gas chromatograms of cyclohexane oxidation products cyclohexanol and cyclohexanone, with peaks at 6.127 min and 6.288 min, respectively. Figure 4 The image shows the gas chromatograms of cyclohexanol and cyclohexanone obtained in Example 42 of this invention. The formation of cyclohexanol (6.185 min) and cyclohexanone (6.347 min) is clearly visible, indicating that the product generated by catalytic oxidation in this invention is the product described above.

[0103] Example 43: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 200 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@16 (1.0 mg) was dispersed in cyclohexane (84.16 g, 1.0 mol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to a gas chromatographic analyzer. GC analysis was performed using standard toluene (0.1842 g, 2.0 mmol) to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol), an internal standard for liquid chromatography, was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 5.2%, a cyclohexanol selectivity of 46%, a cyclohexanone selectivity of 51%, and an adipic acid selectivity of 3%. Glutaric acid and other byproducts were not detected.

[0104] Example 44: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6 (2.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 7.8%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 50%, and an adipic acid selectivity of 3%. Glutaric acid and other byproducts were not detected.

[0105] Example 45: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6 (200.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 16.8%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 49%, adipic acid selectivity of 3%, and glutaric acid selectivity of 1%.

[0106] Example 46: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 80 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas chromatogram. Toluene (0.1842 g, 2.0 mmol) was used as an internal standard for GC analysis to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) was added as an internal standard for liquid chromatography for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 11.2%, a cyclohexanol selectivity of 49%, a cyclohexanone selectivity of 49%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0107] Example 47: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 110 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 13.2%, a cyclohexanol selectivity of 48%, a cyclohexanone selectivity of 50%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0108] Example 48: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 140 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 16.8%, a cyclohexanol selectivity of 46%, a cyclohexanone selectivity of 48%, adipic acid selectivity of 4%, and glutaric acid selectivity of 2%.

[0109] Example 49: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 160 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 17.0%, a cyclohexanol selectivity of 45%, a cyclohexanone selectivity of 48%, adipic acid selectivity of 5%, and glutaric acid selectivity of 2%.

[0110] Example 50: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@2 0- F（Ⅳ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 0.5 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 12.4%, a cyclohexanol selectivity of 50%, a cyclohexanone selectivity of 48%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0111] Example 51: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 0.8 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 15.4%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 50%, and an adipic acid selectivity of 3%. Glutaric acid and other byproducts were not detected.

[0112] Example 52: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@2 0- F（Ⅳ）@0.01@100@5@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.5 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 16.5%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 49%, adipic acid selectivity of 3%, and glutaric acid selectivity of 1%.

[0113] Example 53: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 6.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for another 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 12.4%, a cyclohexanol selectivity of 53%, a cyclohexanone selectivity of 55%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0114] Example 54: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 12.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 16.2%, a cyclohexanol selectivity of 46%, a cyclohexanone selectivity of 50%, adipic acid selectivity of 3%, and glutaric acid selectivity of 1%.

[0115] Example 55: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 15.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 16.8%, a cyclohexanol selectivity of 46%, a cyclohexanone selectivity of 48%, adipic acid selectivity of 4%, and glutaric acid selectivity of 2%.

[0116] Example 56: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 24.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 17.2%, a cyclohexanol selectivity of 45%, a cyclohexanone selectivity of 47%, adipic acid selectivity of 5%, and glutaric acid selectivity of 3%.

[0117] Example 57: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅴ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 13.2%, a cyclohexanol selectivity of 49%, a cyclohexanone selectivity of 49%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0118] Example 58: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅵ）@0.01@100@5@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 14.4%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 51%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0119] Example 59: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅵ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 15.2%, a cyclohexanol selectivity of 48%, a cyclohexanone selectivity of 50%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0120] Example 60: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅶ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 13.5%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 51%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0121] Example 61: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (TLT) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅷ）@0.01@100@5@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 14.6%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 51%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0122] Example 62: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅸ）@0.01@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 15.0%, a cyclohexanol selectivity of 49%, a cyclohexanone selectivity of 49%, and an adipic acid selectivity of 2%. Glutaric acid and other byproducts were not detected.

[0123] Example 63: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.0001@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 11.4%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 46%, adipic acid selectivity of 4%, and glutaric acid selectivity of 3%.

[0124] Example 64: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.001@100@5@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 13.6%, a cyclohexanol selectivity of 46%, a cyclohexanone selectivity of 47%, adipic acid selectivity of 4%, and glutaric acid selectivity of 3%.

[0125] Example 65: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (TLT) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.1@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 15.6%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 50%, and an adipic acid selectivity of 3%. Glutaric acid and other byproducts were not detected.

[0126] Example 66: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@1@100@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 16.5%, a cyclohexanol selectivity of 48%, a cyclohexanone selectivity of 49%, and an adipic acid selectivity of 3%. Glutaric acid and other byproducts were not detected.

[0127] Example 67: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.01@10@5@90@16. (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the temperature reached the set temperature, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 11.0%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 49%, and an adipic acid selectivity of 4%. Glutaric acid and other byproducts were not detected.

[0128] Example 68: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.01@200@5@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analysis showed a cyclohexane conversion rate of 15.4%, a cyclohexanol selectivity of 49%, a cyclohexanone selectivity of 48%, and an adipic acid selectivity of 3%. Glutaric acid and other byproducts were not detected.

[0129] Example 69: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@0.01@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 11.4%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 47%, adipic acid selectivity of 3%, and glutaric acid selectivity of 3%.

[0130] Example 70: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@1@90@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 15.4%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 50%, and an adipic acid selectivity of 3%. Glutaric acid and other byproducts were not detected.

[0131] Example 71: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@10@90@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 15.9%, a cyclohexanol selectivity of 48%, a cyclohexanone selectivity of 49%, and an adipic acid selectivity of 3%. Glutaric acid and other byproducts were not detected.

[0132] Example 72: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@5@30@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 8.4%, a cyclohexanol selectivity of 46%, a cyclohexanone selectivity of 45%, adipic acid selectivity of 5%, and glutaric acid selectivity of 4%.

[0133] Example 73: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (TLT) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@5@80@16 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 12.4%, a cyclohexanol selectivity of 49%, a cyclohexanone selectivity of 47%, adipic acid selectivity of 3%, and glutaric acid selectivity of 1%.

[0134] Example 74: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@12 - F（Ⅳ）@0.01@100@5@120@1 6 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 15.8%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 48%, adipic acid selectivity of 3%, and glutaric acid selectivity of 2%.

[0135] Example 75: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite (CTTL) in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the CTTL catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@ 6. (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 11.5%, a cyclohexanol selectivity of 47%, a cyclohexanone selectivity of 46%, adipic acid selectivity of 4%, and glutaric acid selectivity of 3%.

[0136] Example 76: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2- F（Ⅳ）@0.01@100@5@90@24 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was added to a 100 mL volumetric flask. 10 mL of the solution was accurately transferred to the final volume and added to the gas phase separator. GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard to determine the conversion rate of the substrate cyclohexane, and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion rate of 15.6%, a cyclohexanol selectivity of 46%, a cyclohexanone selectivity of 50%, and an adipic acid selectivity of 4%. Glutaric acid and other byproducts were not detected.

[0137] Comparative Example 1: This example illustrates the application of a fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones. The difference from Example 1 is that the specific implementation involves placing the fluorocarbon-modified cobalt-nickel-aluminum hydrotalcite catalyst in a 100 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner. LDH-Co 0.15 & 20 Ni 0.15 & 20 Al 0.1 & 20 AT 0.8 & 20 @120@1 2 (20.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 130 °C with stirring. When the set temperature was reached, oxygen was introduced to 1.0 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and then stirred at room temperature for 6.0 h to completely decompose and convert the small amount of residual cycloalkyl hydrogen peroxide. After the reaction was completed, the residual gas was slowly released, the reaction vessel was opened, and acetone was brought to a final volume of 100 mL in a volumetric flask. 10 mL of the final volume solution was accurately transferred and added... GC analysis was performed using toluene (0.1842 g, 2.0 mmol) as the internal standard for gas chromatography to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone. 10 mL of the solution was accurately transferred to a final volume, and benzoic acid (0.1221 g, 1.0 mmol) as the internal standard for liquid chromatography was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. GC and HPLC analyses showed a cyclohexane conversion of 8.8%, a cyclohexanol selectivity of 43%, a cyclohexanone selectivity of 42%, adipic acid selectivity of 8%, and glutaric acid selectivity of 7%.

[0138] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain, characterized in that: The cobalt-nickel-aluminum hydrotalcite contains ions such as Co... 2+ Ni 2+ And Al 3+ The fluorocarbon chain is made of at least one compound of formula (I) to (III); ； Among them, the Each is independently selected from C1 to C6 alkoxy groups.

2. The cobalt-nickel-aluminum hydrotalcite modified with a fluorocarbon chain according to claim 1, characterized in that: The fluorocarbon chain is made of at least one compound of formulas (IV) to (IX); 。 3. The method for preparing a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite according to any one of claims 1 to 2, characterized in that: Includes the following steps, S1 first Co 2+ Aqueous solution, Ni 2+ Aqueous solution, Al 3+ The aqueous solution and the urea aqueous solution were stirred and mixed under an inert gas atmosphere, and then subjected to a hydrothermal reaction. After the reaction was completed, the cobalt-nickel-aluminum hydrotalcite was obtained through post-treatment. S2 first disperses the cobalt-nickel-aluminum hydrotalcite obtained in S1 in anhydrous toluene, and then reacts it with at least one of the compounds in formulas (I) to (III) in an inert gas atmosphere under the action of triethylamine. After the reaction is completed, the cobalt-nickel-aluminum hydrotalcite modified with fluorocarbon chain is obtained.

4. The method for preparing a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite according to claim 3, characterized in that: In S1, Co is controlled 2+ The concentration of the aqueous solution is 0.01~10.00 mol / L, Ni 2+ The concentration of the aqueous solution is 0.01~10.00 mol / L, Al 3+ The concentration of the aqueous solution is 0.01~10.00mol / L, and the concentration of the urea aqueous solution is 0.01~20.00mol / L.

5. The method for preparing a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite according to claim 1, characterized in that: In S1, Co 2+ Ni 2+ The molar ratio is 1:(0.10~10.00), Co 2+ and Ni 2+ Al 3+ The molar ratio is 1:(0.01~100.00), Co 2+ and Ni 2+ And Al 3+ The molar ratio of urea is 1:(0.01~100.00).

6. The method for preparing a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite according to claim 1, characterized in that: In S1, the reaction temperature is controlled at 100~200℃ and the reaction time is 8~72h.

7. The method for preparing a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite according to claim 1, characterized in that: In S2, the ratio of cobalt-nickel-aluminum hydrotalcite, at least one compound of formula (I) to (III) above, anhydrous toluene, and triethylamine is controlled to be 1g: (0.0001~1.0000)mol: (10~200)mL: (0.01~10.00)g.

8. The method for preparing a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite according to claim 1, characterized in that: In S2, the reaction temperature is controlled at 30~120℃ and the reaction time is controlled at 6~96h.

9. The application of a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite according to any one of claims 1 to 2 in the catalytic partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones.

10. The application of a carbon-fluorine chain modified cobalt-nickel-aluminum hydrotalcite according to claim 9, characterized in that: The specific implementation method for the partial oxidation of cycloalkanes to prepare cycloalkyl alcohols and cycloalkyl ketones is as follows: after dispersing cobalt-nickel-aluminum hydrotalcite modified with fluorocarbon chains in cycloalkanes, the mixture is stirred and heated in a sealed reaction system while oxygen is introduced and stirred during the reaction. After the reaction is completed, a reaction mixture containing partially oxidized products cycloalkyl alcohols and cycloalkyl ketones is obtained through post-treatment.

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