Preparation method of hollow structure molybdenum disulfide nano reactor and application in conversion of aromatic phenol and ether

Abstract

This invention discloses a method for preparing a hollow molybdenum disulfide nanoreactor and its application in the conversion of aromatic phenols and ethers. The hollow molybdenum disulfide nanoreactor is denoted as M / MoS2, where M is one of the transition metals Co, Ni, Fe, and Cu, the mass ratio of M / (M+MoS2) is 10wt.%–50wt.%, and MoS2 represents hollow MoS2 nanospheres with a cavity diameter ranging from 70–380 nm. Compared to traditional bulk or nanosheet MoS2 materials, the metal-MoS2 interface strengthening effect caused by the special hollow nanosphere structure enables highly efficient catalysis of the hydrogenation and deoxygenation of aromatic phenols and ethers into aromatic hydrocarbons at 200–250 °C, hydrogen pressure 3–6 MPa, reaction time 3–6 h, and a nanoreactor / substrate mass ratio of 1:5–1:1, achieving a conversion rate >90% and an aromatic hydrocarbon yield >80%.

Description

Technical Field

[0001] This invention belongs to the field of industrial catalysis and bioenergy conversion technology, and specifically relates to a novel catalyst and preparation method for the catalytic hydrogenation and deoxygenation of aromatic phenols and ether compounds to prepare aromatic hydrocarbons. Background Technology

[0002] Biomass is the only renewable carbon resource that can be used to produce liquid biofuels, and fully utilizing renewable biomass resources will help alleviate the fossil fuel crisis. Lignin, due to its unique aromatic structure, has a natural advantage in preparing high-value-added aromatic hydrocarbons. Therefore, how to achieve the efficient conversion of lignin into aromatic hydrocarbons is a cutting-edge scientific issue in the field of biomass utilization. Currently, because the structure of real lignin is too complex and difficult to dissolve, using aromatic phenols and ethers with typical lignin functional groups as model compounds for the catalytic conversion of lignin has become the mainstream approach. Therefore, achieving the efficient conversion of aromatic phenols and ethers into aromatic hydrocarbons is of great significance.

[0003] Compared to metal and noble metal catalysts, sulfide catalysts, represented by molybdenum disulfide (MoS2), have proven to be economical, sulfur-resistant, and highly efficient hydrodeoxygenation catalysts due to their unique advantage in balancing hydrogenation and deoxygenation capabilities, enabling the preparation of aromatic compounds from aromatic phenols and ethers (Chem Rev, 2015, 115, 11559-624). However, they suffer from low substrate conversion and low aromatic yields. Therefore, developing novel MoS2 catalysts is an effective way to achieve efficient conversion of aromatic phenols and ethers.

[0004] The literature (J. Energy Chem. 2023, 77, 601–631) summarizes the modification strategies of MoS2 catalysts, finding that they mainly fall into two categories: 1) Single-metal MoS2 catalysts: two strategies are used, namely micromorphological control (number of stacked layers, plate size, appearance structure, etc.) and defect engineering, both aiming to increase the number of S vacancies, thereby improving their hydrodeoxygenation activity. 2) Bifunctional modified MoS2-based catalysts: metal doping, acid modification, and support control strategies.

[0005] Unfortunately, current research on the hydrodeoxygenation of aromatic phenols and ethers on MoS2-based catalysts focuses on the control of the composition and nanostructure of active sites, lacking research on the control of the reaction microenvironment. The role of active site control in catalyst activity and selectivity is undeniable, but typical heterogeneous catalytic reactions must also consider molecular adsorption and diffusion effects (Angew. Chem. 2023, 62, e2022136). In recent years, nanoreactors, represented by hollow carbon spheres, silica nanospheres, and periodically ordered mesoporous silica, have been widely used in heterogeneous catalytic reactions (ACS Sustainable Chem. Eng. 2021, 9, 2990-3010). Studies have shown that the unique cavity structure of nanoreactors provides substrate enrichment and diffusion enhancement effects for catalytic reactions, significantly increasing reaction rates. Achieving a balance between substrate enrichment and diffusion effects by controlling the cavity size of nanoreactors is a key means to achieve efficient conversion (ACS Catal. 2019, 9, 2969-2976). In addition, other microenvironment regulation effects mediated by nanoreactors, such as active component-support interaction, molecular sieve effect, spatial isolation effect, and active component stabilization effect, are also beneficial to catalytic reactions.

[0006] Therefore, based on the ability of nanoreactors to regulate the reaction microenvironment, this invention develops a method for preparing a hollow molybdenum disulfide nanoreactor and applies it to the hydrodeoxygenation reaction of aromatic phenols and ethers to produce aromatics. This technology solves the problems of low substrate conversion and low aromatic yield in current technologies, achieving a significant improvement in substrate conversion >90% and aromatic yield >80%. Summary of the Invention

[0007] This invention provides a method for preparing a hollow molybdenum disulfide nanoreactor and its application in catalyzing the hydrogenation and deoxygenation of aromatic phenols and ethers to produce aromatic hydrocarbons.

[0008] This invention aims to improve the substrate conversion rate and aromatic product yield of the hydrodeoxygenation reaction of aromatic phenols and ethers catalyzed by molybdenum disulfide-based catalysts. Based on the control of the reaction microenvironment by nanoreactors, a strategy for preparing hollow molybdenum disulfide nanoreactors assisted by amino-modified SiO2 hard template method was developed, which achieved a significant improvement in conversion rate and yield.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] A hollow molybdenum disulfide nanoreactor, denoted as M / MoS2, wherein M is one of the transition metals Co, Ni, Fe, and Cu, the mass ratio of M / (M+MoS2) is 10wt.%-50wt.%, and MoS2 represents MoS2 nanospheres with a hollow structure, the cavity diameter of which ranges from 70 to 380 nm.

[0011] The method for preparing the hollow molybdenum disulfide nanoreactor of the present invention includes the following steps:

[0012] a) Weigh SiO2 nanospheres and 3-aminopropyltriethoxysilane and place them in a methanol solution and stir continuously until a uniform suspension is formed; after the suspension is completed, filter to obtain a solid and wash it several times with ethanol, and then dry to obtain amino-modified SiO2 nanospheres, i.e. N-SiO2.

[0013] b) Add the above N-SiO2 to ethylene glycol and sonicate it to disperse it evenly; add deionized water and stir continuously until a uniform suspension is formed; then add ammonium tetrathiomolybdate and stir for 1-3 hours; after the end, the solution is rotary evaporated and dried to obtain a reddish-brown powder; calcine the reddish-brown powder at 400-600℃ under a nitrogen atmosphere for 2-6 hours to obtain MoS2 / N-SiO2;

[0014] c) MoS2 / N-SiO2 was treated with 10-20 wt.% HF solution at room temperature for 12-24 h to etch away SiO2; after etching, the solid was separated, washed multiple times with water and anhydrous ethanol, and vacuum dried to obtain hollow MoS2 nanospheres.

[0015] d) Weigh the above MoS2 and metal M salt and dissolve them in anhydrous ethanol. After stirring evenly, transfer the solution to a polytetrafluoroethylene hydrothermal reactor and react at 120-180℃ for 1-5 hours. After the reaction is completed, allow it to cool naturally to room temperature, filter and separate to obtain a black solid. Wash it several times with deionized water and ethanol and then perform vacuum drying to obtain M / MoS2 loaded with metal M particles.

[0016] The diameter of the SiO2 nanospheres ranges from 70 to 380 nm, the concentration of SiO2 in the methanol solution is 0.03 to 0.045 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 2:1 to 1:2.

[0017] The concentration of N-SiO2 in ethylene glycol ranges from 0.4 to 1.2 g / mL, the volume ratio of ethylene glycol to deionized water is 1:20 to 1:10, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate is 2:1 to 1:2.

[0018] The concentration of MoS2 in anhydrous ethanol is 1.25-2.5 mg / mL, and the metal M salt is one of nitrate, sulfate, or acetate, and the mass is weighed according to the mass ratio of M / (M+MoS2) of 10wt.%-50wt.%.

[0019] The application of the hollow molybdenum disulfide nanoreactor of the present invention in the conversion of aromatic phenols and ethers.

[0020] The application of the hollow molybdenum disulfide nanoreactor of the present invention in the conversion of aromatic phenols and ethers includes the following steps:

[0021] a) After thoroughly mixing the reaction substrate, nanoreactor, internal standard and reaction solvent, add them to the reaction vessel, seal it and replace the air in the vessel with hydrogen. Then fill the pressure in the vessel with hydrogen to the target pressure of 3MPa to 5MPa.

[0022] b) Heat the reactor to 200℃~250℃ and start stirring. The reaction time is 3h-6h.

[0023] c) After the reaction is complete, stop stirring and cool to room temperature. Then, release the pressure and open the vessel to separate the liquid product and the nanoreactor. Use mass spectrometry-gas chromatography to perform qualitative and quantitative analysis on the liquid product and calculate the substrate conversion rate and aromatic product yield.

[0024] The hollow molybdenum disulfide nanoreactor is used in the conversion of aromatic phenols and ethers. The substrate for the reaction of aromatic phenols and ethers is one of p-cresol, guaiacol, diphenyl ether, and 2-aryloxy-1-arylethanol. The mass ratio of the nanoreactor to the substrate is 1:5 to 1:1. The reaction solvent is one of n-pentane, n-hexane, and n-heptane.

[0025] The significant advantages of this invention are:

[0026] 1. The hollow molybdenum disulfide nanoreactor of this invention is prepared using conventional and inexpensive chemicals as raw materials, which is low in cost and the preparation process is simple and easy to carry out, with less time, material consumption and energy consumption.

[0027] 2. The hollow molybdenum disulfide nanoreactor of the present invention has significant novel structural features, namely, metal M nanoparticles are loaded on the surface of hollow MoS2 nanospheres.

[0028] 3. The hollow molybdenum disulfide nanoreactor described in this invention exhibits excellent activity in the hydrodeoxygenation of aromatic phenols and ethers to produce aromatic hydrocarbons. Compared with traditional bulk or nanosheet MoS2 materials, the unique hollow nanosphere structure of this nanoreactor, which enhances the metal-MoS2 interface and enriches the substrate and enhances diffusion during the reaction process, significantly improves its catalytic activity and reaction rate. At a reaction temperature of 200°C, the conversion rate of phenolic ether compounds is >90%, and the yield of single aromatic products is >80%. Attached Figure Description

[0029] Figure 1 The images are transmission electron microscopy (TEM) images of the Co / MoS2 nanoreactor samples described in Examples 1-3. Detailed Implementation

[0030] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.

[0031] Example 1

[0032] Preparation of 10 wt.% Co / MoS2-70 nm nanoreactors

[0033] a) Weigh 1.8 g of SiO2 nanospheres with a particle diameter of 70 nm and 33.54 g of 3-aminopropyltriethoxysilane into 40 mL of methanol solution and stir continuously until a homogeneous suspension is formed (the concentration of SiO2 in the methanol solution is 0.045 g).

[0034] (g / mL, the molar ratio of SiO2 to 3-aminopropyltriethoxysilane was 2:1). After completion, the solid was filtered and washed several times with ethanol, and then dried to obtain amino-modified SiO2 nanospheres, namely N-SiO2-70 nm.

[0035] b) 1.2 g of N-SiO2-70 nm was added to 1 mL of ethylene glycol solution and ultrasonically dispersed. 20 mL of deionized water was added to the solution, and the mixture was stirred continuously until a homogeneous suspension was formed. Then, 0.6 g of ammonium tetrathiomolybdate was added and stirred for 1 h (the concentration of N-SiO2 in ethylene glycol was 1.2 g / mL, the volume ratio of ethylene glycol to deionized water was 1:20, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate was 2:1). After this, the solution was transferred to a pear-shaped flask, the water was evaporated, and then dried to obtain a reddish-brown powder. The reddish-brown powder was calcined at 400 °C under a nitrogen atmosphere for 2 h to obtain MoS2 / N-SiO2-70 nm.

[0036] c) MoS2 / N-SiO2-70 nm was treated with 10 wt.% HF solution at room temperature for 24 h to etch away SiO2. After etching, the solid was separated, washed with water and anhydrous ethanol, and vacuum dried to obtain MoS2-70 nm.

[0037] d) Weigh 100 mg of MoS2-70 nm and dissolve it together with 47 mg of cobalt acetate tetrahydrate in 40 mL of anhydrous ethanol (the concentration of MoS2 in anhydrous ethanol is 2.5 mg / mL, and the mass ratio of M / (M+MoS2) is 10 wt.%). After stirring evenly, transfer the solution to a 100 mL polytetrafluoroethylene hydrothermal reactor and react at 120 °C for 1 h. After the reaction is complete, allow it to cool naturally to room temperature, filter to separate the black solid, wash with anhydrous ethanol, and then vacuum dry to obtain 10

[0038] wt.% Co / MoS2-70 nm black powder.

[0039] Instructions attached Figure 1 'a' contains a TEM image of the 10wt.% Co / MoS2-70 nm nanoreactor sample described in this embodiment, verifying its unique hollow nanosphere structure. Through measurement and statistics, the cavity diameter of the MoS2 hollow nanospheres prepared under these conditions is approximately 70 nm, indicating that the size of the formed MoS2 hollow nanospheres is consistent with the size of the hard template SiO2 nanospheres.

[0040] Example 2

[0041] Preparation of 30wt.% Co / MoS2-250 nm nanoreactors

[0042] a) Weigh 1.8 g of SiO2 nanospheres with a particle diameter of 250 nm and 67.08 g of 3-aminopropyltriethoxysilane into 50 mL of methanol solution and stir continuously until a uniform suspension is formed (the concentration of SiO2 in the methanol solution is 0.036 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 1:1). After completion, wash with ethanol and then dry to obtain amino-modified SiO2 nanospheres, i.e., N-SiO2-250 nm;

[0043] b) Add 0.8 g of N-SiO2-250 nm to 1 mL of ethylene glycol solution and sonicate to disperse it evenly. Add 15 mL of deionized water to the above solution and stir continuously until a uniform suspension is formed. Then, add 0.8 g of ammonium tetrathiomolybdate and stir for 2 h (the concentration of N-SiO2 in ethylene glycol is 0.8 g / mL, the volume ratio of ethylene glycol to deionized water is 1:15, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate is 1:1). After completion, transfer the solution to a pear-shaped flask, evaporate the water, and dry to obtain a reddish-brown powder. Calcine the reddish-brown powder at 500 °C under a nitrogen atmosphere for 4 h to obtain MoS2 / N-SiO2-250 nm;

[0044] c) MoS2 / N-SiO2-250 nm was treated with 15 wt.% HF solution at room temperature for 18 h to etch away SiO2. After etching, the solid was separated, washed with water and anhydrous ethanol, and vacuum dried to obtain MoS2-250 nm.

[0045] d) Weigh 100 mg of MoS2-70 nm and dissolve it together with 181 mg of cobalt acetate tetrahydrate in 50 mL of anhydrous ethanol (the concentration of MoS2 in anhydrous ethanol is 2 mg / mL, and the mass ratio of M / (M+MoS2) is 30 wt.%). After stirring evenly, transfer the solution to a 100 mL polytetrafluoroethylene hydrothermal reactor and react at 150 °C for 3 h. After the reaction is complete, allow it to cool naturally to room temperature, filter to separate the black solid, wash with anhydrous ethanol, and then vacuum dry to obtain 30

[0046] wt.% Co / MoS2-250 nm black powder.

[0047] Instructions attached Figure 1 b contains a TEM image of the 30wt.% Co / MoS2-250 nm nanoreactor sample described in this embodiment, which verifies its unique hollow nanosphere structure. Through measurement and statistics, the cavity diameter of the MoS2 hollow nanospheres prepared under this condition is approximately 250 nm, further verifying that the size of the formed MoS2 hollow nanospheres is consistent with the size of the hard template SiO2 nanospheres.

[0048] Example 3

[0049] Preparation of 50 wt.% Co / MoS2-380 nm nanoreactors

[0050] a) Weigh 1.8 g of SiO2 nanospheres with a particle diameter of 380 nm and 134.16 g of 3-aminopropyltriethoxysilane into 60 mL of methanol solution and stir continuously until a uniform suspension is formed (the concentration of SiO2 in the methanol solution is 0.03 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 1:2). After completion, wash with ethanol and then dry to obtain amino-modified SiO2 nanospheres, i.e., N-SiO2-380 nm;

[0051] b) Add 0.4 g of N-SiO2-380 nm to 1 mL of ethylene glycol solution and sonicate to disperse it evenly. Add 10 mL of deionized water to the above solution and stir continuously until a uniform suspension is formed. Then, add 0.8 g of ammonium tetrathiomolybdate and stir for 3 h (the concentration of N-SiO2 in ethylene glycol is 0.4 g / mL, the volume ratio of ethylene glycol to deionized water is 1:10, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate is 1:2). After completion, transfer the solution to a pear-shaped flask, evaporate the water by rotary evaporation, and dry to obtain a reddish-brown powder. Calcine the reddish-brown powder at 600 °C under a nitrogen atmosphere for 6 h to obtain MoS2 / N-SiO2-380 nm;

[0052] c) MoS2 / N-SiO2-380 nm was etched away by treating with 20 wt.% HF solution at room temperature for 12 h. After etching, the solid was separated, washed with water and anhydrous ethanol, and vacuum dried to obtain MoS2-380 nm.

[0053] d) Weigh 100 mg of MoS2-380 nm and dissolve it together with 422 mg of cobalt acetate tetrahydrate in 80 mL of anhydrous ethanol (the concentration of MoS2 in anhydrous ethanol is 1.25 mg / mL, and the mass ratio of M / (M+MoS2) is 50 wt.%). After stirring evenly, transfer the solution to a 100 mL polytetrafluoroethylene hydrothermal reactor and react at 180 °C for 5 h. After the reaction is complete, allow it to cool naturally to room temperature, filter to separate the black solid, wash with anhydrous ethanol, and then vacuum dry to obtain 50

[0054] wt.% Co / MoS2-250 nm black powder.

[0055] Instructions attached Figure 1 c contains a TEM image of the 50wt.% Co / MoS2-380 nm nanoreactor sample described in this embodiment, which verifies its unique hollow nanosphere structure. Through measurement and statistics, the cavity diameter of the MoS2 hollow nanospheres prepared under these conditions is approximately 380 nm, further demonstrating that the size of the formed MoS2 hollow nanospheres is consistent with the size of the hard template SiO2 nanospheres.

[0056] Example 4

[0057] Preparation of 30wt.% Co / MoS2-140 nm nanoreactors

[0058] a) Weigh 1.8 g of SiO2 nanospheres with a particle diameter of 140 nm and 101.25 g of 3-aminopropyltriethoxysilane into 45 mL of methanol solution and stir continuously until a homogeneous suspension is formed (the concentration of SiO2 in the methanol solution is 0.04 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 1:1.5). After completion, wash with ethanol and then dry to obtain amino-modified SiO2 nanospheres, i.e., N-SiO2-140 nm;

[0059] b) 0.6 g of N-SiO2-250 nm was added to 1 mL of ethylene glycol solution and ultrasonically dispersed until homogeneous. 10 mL of deionized water was added to the solution, and stirring was continued until a homogeneous suspension was formed. Subsequently, 0.9 g of ammonium tetrathiomolybdate was added and stirred for 1.5 h (the concentration of N-SiO2 in ethylene glycol was 0.6 g / mL, the volume ratio of ethylene glycol to deionized water was 1:10, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate was 1:1.5). Afterward, the solution was transferred to a pear-shaped flask, the water was evaporated, and then dried to obtain a reddish-brown powder. The reddish-brown powder was calcined at 450 °C under a nitrogen atmosphere for 4 h to obtain MoS2 / N-SiO2-140 nm.

[0060] c) MoS2 / N-SiO2-140 nm was treated with 15 wt.% HF solution at room temperature for 15 h to etch away SiO2. After etching, the solid was separated, washed with water and anhydrous ethanol, and vacuum dried to obtain MoS2-140 nm.

[0061] d) Weigh 100 mg of MoS2-140 nm and dissolve it together with 212 mg of cobalt nitrate hexahydrate in 50 mL of anhydrous ethanol (the concentration of MoS2 in anhydrous ethanol is 2 mg / mL, and the mass ratio of M / (M+MoS2) is 30 wt.%). After stirring evenly, transfer the solution to a 100 mL polytetrafluoroethylene hydrothermal reactor and react at 140 °C for 3 h. After the reaction is completed, allow it to cool naturally to room temperature, filter to separate the black solid, wash with anhydrous ethanol, and then vacuum dry to obtain 30 wt.% Co / MoS2-140 nm black powder.

[0062] Example 5

[0063] Preparation of 30wt.% Co / MoS2-200 nm nanoreactors

[0064] a) Weigh 1.8 g of SiO2 nanospheres with a particle diameter of 200 nm and 45 g of 3-aminopropyltriethoxysilane into 55 mL of methanol solution and stir continuously until a uniform suspension is formed (the concentration of SiO2 in the methanol solution is 0.033 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 1.5:1). After completion, wash with ethanol and then dry to obtain amino-modified SiO2 nanospheres, i.e., N-SiO2-200 nm;

[0065] b) 1 g of N-SiO2-200 nm was added to 1 mL of ethylene glycol solution and ultrasonically dispersed until homogeneous. 20 mL of deionized water was added to the solution, and stirring was continued until a homogeneous suspension was formed. Then, 0.67 g of ammonium tetrathiomolybdate was added and stirred for 2.5 h (the concentration of N-SiO2 in ethylene glycol was 1 g / mL, the volume ratio of ethylene glycol to deionized water was 1:20, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate was 1.5:1). After this, the solution was transferred to a pear-shaped flask, the water was evaporated, and then dried to obtain a reddish-brown powder. The reddish-brown powder was calcined at 550 °C under a nitrogen atmosphere for 3 h to obtain MoS2 / N-SiO2-200 nm.

[0066] c) MoS2 / N-SiO2-250 nm was treated with 20 wt.% HF solution at room temperature for 12 h to etch away SiO2. After etching, the solid was separated, washed with water and anhydrous ethanol, and vacuum dried to obtain MoS2-200 nm;

[0067] d) Weigh 100 mg of MoS2-200 nm and dissolve it together with 204 mg of cobalt sulfate heptahydrate in 60 mL of anhydrous ethanol (the concentration of MoS2-y in anhydrous ethanol is 1.67 mg / mL, and the mass ratio of M / (M+MoS2) is 30 wt.%). After stirring evenly, transfer the solution to a 100 mL polytetrafluoroethylene hydrothermal reactor and react at 120 °C for 3 h. After the reaction is complete, allow it to cool naturally to room temperature, filter to separate the black solid, wash with anhydrous ethanol, and then vacuum dry to obtain 30 wt.% Co / MoS2-200 nm black powder.

[0068] Example 6

[0069] Preparation of 30 wt.% Ni@MoS2-250 nm nanoreactor

[0070] a) Weigh 1.8 g of SiO2 nanospheres with a particle diameter of 250 nm and 67.08 g of 3-aminopropyltriethoxysilane into 60 mL of methanol solution and stir continuously until a uniform suspension is formed (the concentration of SiO2 in the methanol solution is 0.03 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 1:1). After completion, wash with ethanol and then dry to obtain amino-modified SiO2 nanospheres, i.e., N-SiO2-250 nm.

[0071] b) Add 0.6 g of N-SiO2-250 nm to 1 mL of ethylene glycol solution and sonicate to disperse it evenly. Add 10 mL of deionized water to the above solution and stir continuously until a uniform suspension is formed. Then, add 0.12 g of ammonium tetrathiomolybdate and stir for 2 h (the concentration of N-SiO2 in ethylene glycol is 0.6 g / mL, the volume ratio of ethylene glycol to deionized water is 1:10, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate is 1:2). After completion, transfer the solution to a pear-shaped flask, evaporate the water by rotary evaporation, and dry to obtain a reddish-brown powder. Calcine the reddish-brown powder at 400 °C under a nitrogen atmosphere for 6 h to obtain MoS2 / N-SiO2-250 nm;

[0072] c) MoS2 / N-SiO2-250 nm was etched away by treating with 10 wt.% HF solution at room temperature for 18 h. After etching, the solid was separated, washed with water and anhydrous ethanol, and vacuum dried to obtain MoS2-320 nm.

[0073] d) Weigh 100 mg of MoS2-250 nm and dissolve it together with 182 mg of nickel acetate tetrahydrate in 40 mL of anhydrous ethanol (the concentration of MoS2 in anhydrous ethanol is 2.5 mg / mL, and the mass ratio of M / (M+MoS2) is 30 wt.%). After stirring evenly, transfer the solution to a 100 mL polytetrafluoroethylene hydrothermal reactor and react at 140 °C for 1 h. After the reaction is complete, allow it to cool naturally to room temperature, filter to separate the black solid, wash with anhydrous ethanol, and then vacuum dry to obtain 30 wt.% Co / MoS2-250 nm black powder.

[0074] Example 7

[0075] Preparation of 30 wt.% Fe@MoS2-250 nm nanoreactor

[0076] a) Weigh 1.8 g of SiO2 nanospheres with a particle diameter of 250 nm and 67.08 g of 3-aminopropyltriethoxysilane into 40 mL of methanol solution and stir continuously until a uniform suspension is formed (the concentration of SiO2 in the methanol solution is 0.045 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 1:1). After completion, wash with ethanol and then dry to obtain amino-modified SiO2 nanospheres, i.e., N-SiO2-250 nm;

[0077] b) 1.2 g of N-SiO2-250 nm was added to 1 mL of ethylene glycol solution and ultrasonically dispersed until homogeneous. 15 mL of deionized water was added to the solution, and stirring was continued until a homogeneous suspension was formed. Subsequently, 0.8 g of ammonium tetrathiomolybdate was added and stirred for 2 h (the concentration of N-SiO2 in ethylene glycol was 0.6 g / mL, the volume ratio of ethylene glycol to deionized water was 1:15, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate was 1.5:1). After completion, the solution was transferred to a pear-shaped flask, the water was evaporated, and then dried to obtain a reddish-brown powder. The reddish-brown powder was calcined at 600 °C under a nitrogen atmosphere for 2 h to obtain MoS2 / N-SiO2-250 nm.

[0078] c) MoS2 / N-SiO2-250 nm was treated with 18 wt.% HF solution at room temperature for 10 h to etch away SiO2. After etching, the solid was separated, washed with water and anhydrous ethanol, and vacuum dried to obtain MoS2-250 nm.

[0079] d) Weigh 100 mg of MoS2-70 nm and dissolve it together with 149 mg of ferric acetate in 40 mL of anhydrous ethanol (the concentration of MoS2 in anhydrous ethanol is 2.5 mg / mL, and the mass ratio of M / (M+MoS2) is 30 wt.%). After stirring evenly, transfer the solution to a 100 mL polytetrafluoroethylene hydrothermal reactor and react at 130 °C for 2 h. After the reaction is complete, allow it to cool naturally to room temperature, filter to separate the black solid, wash with anhydrous ethanol, and then vacuum dry to obtain a 30 wt.% Co / MoS2-250 nm black powder.

[0080] Example 8

[0081] Preparation of 30 wt.% Cu@MoS2-250 nm nanoreactor

[0082] a) Weigh 1.8 g of SiO2 nanospheres with a particle diameter of 250 nm and 134.16 g of 3-aminopropyltriethoxysilane into 60 mL of methanol solution and stir continuously until a uniform suspension is formed (the concentration of SiO2 in the methanol solution is 0.03 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 1:2). After completion, wash with ethanol and then dry to obtain amino-modified SiO2 nanospheres, i.e., N-SiO2-250 nm;

[0083] b) Add 1 g of N-SiO2-250 nm to 1 mL of ethylene glycol solution and sonicate to disperse it evenly. Add 20 mL of deionized water to the above solution and stir continuously until a uniform suspension is formed. Then, add 1 g of ammonium tetrathiomolybdate and stir for 1 h (the concentration of N-SiO2 in ethylene glycol is 0.5 g / mL, the volume ratio of ethylene glycol to deionized water is 1:15, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate is 1:1). After completion, transfer the solution to a pear-shaped flask, evaporate the water by rotary evaporation, and dry to obtain a reddish-brown powder. Calcine the reddish-brown powder at 550 °C under a nitrogen atmosphere for 5 h to obtain MoS2 / N-SiO2-250 nm;

[0084] c) MoS2 / N-SiO2-250 nm was etched away by treating with 20 wt.% HF solution at room temperature for 15 h. After etching, the solid was separated, washed with water and anhydrous ethanol, and vacuum dried to obtain MoS2-250 nm.

[0085] d) Weigh 100 mg of MoS2-70 nm and dissolve it together with 135 mg of acetone monohydrate in 50 mL of anhydrous ethanol (the concentration of MoS2 in anhydrous ethanol is 2 mg / mL, and the mass ratio of M / (M+MoS2) is 30 wt.%). After stirring evenly, transfer the solution to a 100 mL polytetrafluoroethylene hydrothermal reactor and react at 150 °C for 3 h. After the reaction is complete, allow it to cool naturally to room temperature, filter to separate the black solid, wash with anhydrous ethanol, and then vacuum dry to obtain 30

[0086] wt.% Co / MoS2-250 nm black powder.

[0087] The hollow molybdenum disulfide nanoreactor was used in the hydrodeoxygenation reaction of aromatic phenols and ethers to produce aromatic hydrocarbons. p-Cresol, guaiacol, diphenyl ether, and 2-aryloxy-1-arylethanol were selected as reaction substrates. The catalytic activity of the nanoreactor was tested, and the conversion rate of the substrate and the yield of the aromatic products after the reaction were investigated. The hollow molybdenum disulfide nanoreactor achieved a substrate conversion rate >90% and an aromatic hydrocarbon yield >80%. The specific implementation is as follows:

[0088] Example 9

[0089] p-Cresol Hydrogen Deoxygenation Reaction

[0090] a) 27 mg of a 10 wt.% Co / MoS2-250 nm nanoreactor obtained according to Example 1 and 10 mL of a hexane solution containing 0.125 mol / L p-cresol and 0.125 mol / L n-dodecane were added to a 50 mL high-pressure reactor;

[0091] b) Replace the air in the reactor with hydrogen three times, then fill the reactor with hydrogen until the initial pressure is 3 MPa, raise the temperature to 200°C, stir at 1000 r / min, and react for 3 h.

[0092] c) After the reaction is complete, stop stirring and cool to room temperature. Then, release the pressure and open the vessel to separate the liquid product and the nanoreactor. Use mass spectrometry-gas chromatography to perform qualitative and quantitative analysis on the liquid product and calculate the substrate conversion rate and aromatic product yield.

[0093] The calculation formula is as follows:

[0094]

[0095]

[0096] The internal standard used in this technical solution is n-dodecane, and the substrate concentration is 0.125 mol / L.

[0097] The reaction results are shown in Table 1.

[0098] Table 1. Results of p-cresol conversion catalyzed by a 10 wt.% Co / MoS2-250 nm nanoreactor

[0099]

[0100] The results showed that the 10 wt.% Co / MoS2-250 nm nanoreactor efficiently catalyzed the hydrodeoxygenation of p-cresol to toluene at a reaction temperature of 200 °C. Compared with existing technologies, the conversion rate and aromatic yield were significantly improved.

[0101] Example 10

[0102] p-Cresol Hydrogen Deoxygenation Reaction

[0103] The implementation scheme is basically the same as that of Example 9, except that the nanoreactor used is the 30wt.% Co / MoS2-250 nm nanoreactor described in Example 2. 。 The reaction results are shown in Table 2.

[0104] Table 2. Results of p-cresol conversion catalyzed by a 30 wt.% Co / MoS2-250 nm nanoreactor

[0105]

[0106] Example 11

[0107] p-Cresol Hydrogen Deoxygenation Reaction

[0108] The implementation scheme is basically the same as that of Example 9, except that the nanoreactor used is the 50wt.% Co / MoS2-250 nm nanoreactor described in Example 3. 。 The reaction results are shown in Table 3.

[0109] Table 3. Results of p-cresol conversion catalyzed by a 50 wt.% Co / MoS2-250 nm nanoreactor

[0110]

[0111] Example 12

[0112] p-Cresol Hydrogen Deoxygenation Reaction

[0113] The implementation scheme is basically the same as that of Example 9, except that the nanoreactor used is the 30wt.% Co / MoS2-140 nm nanoreactor described in Example 4. 。 The reaction results are shown in Table 4.

[0114] Table 4. Results of p-cresol conversion catalyzed by a 30 wt.% Co / MoS2-140 nm nanoreactor

[0115]

[0116] Example 13

[0117] p-Cresol Hydrogen Deoxygenation Reaction

[0118] The implementation scheme is basically the same as that of Example 9, except that the nanoreactor used is the 30wt.% Co / MoS2-200 nm nanoreactor described in Example 5. 。 The reaction results are shown in Table 5.

[0119] Table 5. Results of p-cresol conversion catalyzed by a 30 wt.% Co / MoS2-200 nm nanoreactor

[0120]

[0121] Example 14

[0122] p-Cresol Hydrogen Deoxygenation Reaction

[0123] The implementation scheme is basically the same as that of Example 9, except that the nanoreactor used is the 30wt.% Ni@MoS2-250 nm nanoreactor described in Example 6. 。 The reaction results are shown in Table 6.

[0124] Table 6. Results of p-cresol conversion catalyzed by a 30 wt.% Ni@MoS2-250 nm nanoreactor

[0125]

[0126] Example 15

[0127] p-Cresol Hydrogen Deoxygenation Reaction

[0128] The implementation scheme is basically the same as that of Example 9, except that the nanoreactor used is the 30wt.% Fe@MoS2-250 nm nanoreactor described in Example 7. 。 The reaction results are shown in Table 7.

[0129] Table 7. Results of p-cresol conversion catalyzed by 30 wt.% Fe@MoS2-250 nm nanoreactor

[0130]

[0131] Example 16

[0132] p-Cresol Hydrogen Deoxygenation Reaction

[0133] The implementation scheme is basically the same as that of Example 9, except that the nanoreactor used is the 30wt.% Cu@MoS2-250 nm nanoreactor described in Example 8. 。 The reaction results are shown in Table 8.

[0134] Table 8. Results of p-cresol conversion catalyzed by a 30 wt.% Cu@MoS2-250 nm nanoreactor

[0135]

[0136] The results in Table 2-8 show that by adjusting the preparation conditions of the nanoreactor within the specified range, the nanoreactor can efficiently catalyze the hydrogenation and deoxygenation of p-cresol to toluene at a reaction temperature of 200℃, with a conversion rate >90% and a toluene yield >80%.

[0137] Example 17

[0138] p-Cresol Hydrogen Deoxygenation Reaction

[0139] The implementation plan is basically the same as that of Example 9, except that the reaction temperature is adjusted from 200℃ to 230 or 250℃. The reaction results are shown in Table 9.

[0140] Table 9. Results of p-cresol conversion catalyzed by a 30 wt.% Co / MoS2-250 nm nanoreactor

[0141]

[0142] Example 18

[0143] p-Cresol Hydrogen Deoxygenation Reaction

[0144] The implementation scheme is basically the same as that of Example 9, except that the amount of nanoreactor is adjusted to 67.5 mg or 135 mg (i.e., the mass ratio of nanoreactor / substrate is 1:2 or 1:1). The reaction results are shown in Table 10.

[0145] Table 10. Results of p-cresol conversion catalyzed by a 30 wt.% Co / MoS2-250 nm nanoreactor

[0146]

[0147] Example 19

[0148] p-Cresol Hydrogen Deoxygenation Reaction

[0149] The implementation plan is basically the same as that of Example 9, except that the reaction time is adjusted from 3h to 4h or 6h. The reaction results are shown in Table 11.

[0150] Table 11. Results of p-cresol conversion catalyzed by a 30 wt.% Co / MoS2-250 nm nanoreactor

[0151]

[0152] Example 20

[0153] p-Cresol Hydrogen Deoxygenation Reaction

[0154] The implementation scheme is basically the same as that of Example 9, except that the initial H2 pressure is adjusted from 3MPa to 4MPa or 6MPa. The reaction results are shown in Table 1.

[0155] Table 12. Results of p-cresol conversion catalyzed by a 30 wt.% Co / MoS2-250 nm nanoreactor

[0156]

[0157]

[0158] Example 21

[0159] p-Cresol Hydrogen Deoxygenation Reaction

[0160] The implementation scheme is basically the same as that of Example 9, except that the reaction solvent is replaced with n-pentane or n-decane. The reaction results are shown in Table 13.

[0161] Table 13. Results of p-cresol conversion catalyzed by a 30wt.% Co / MoS2-250nm nanoreactor

[0162]

[0163] The results in Table 9-13 show that, within the specified reaction conditions (200℃~250℃, hydrogen pressure 3MPa-6MPa, reaction time 3h-6h, nanoreactor / substrate mass 1:5-1:1), the nanoreactor can efficiently catalyze the hydrogenation and deoxygenation of p-cresol to toluene, with a conversion rate >90% and a toluene yield >80%.

[0164] Example 22

[0165] Hydrodeoxygenation reactions of different aromatic phenols and ethers

[0166] The implementation scheme is basically the same as that in Example 9, except that the reaction substrate is replaced with 0.125 mol / L guaiacol, diphenyl ether or 2-aryloxy-1-arylethanol. The reaction results are shown in Table 14.

[0167] Table 14. Results of p-cresol conversion catalyzed by a 30wt.% Co / MoS2-250nm nanoreactor

[0168]

[0169] Table 14 shows that the nanoreactor exhibits high catalytic activity for the hydrodeoxygenation of various aromatic phenols and ethers to produce aromatics. Substrate conversion is >90%, and aromatic yield is >80%.

[0170] The technical solutions disclosed and proposed in this invention can be implemented by those skilled in the art by appropriately modifying the conditions and routes, etc. Although the methods and preparation techniques of this invention have been described through preferred embodiments, those skilled in the art can obviously modify or recombine the methods and technical routes described herein without departing from the content, spirit, and scope of this invention to achieve the final preparation technique. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included within the spirit, scope, and content of this invention.

Claims

1. The application of a hollow molybdenum disulfide nanoreactor in the hydrodeoxygenation of aromatic phenols or ethers to produce aromatic hydrocarbons, characterized in that, The nanoreactor is represented by M / MoS2, where M is one of the transition metals Co, Ni, Fe, and Cu, and the mass ratio of M / (M+MoS2) is 10-50 wt.%; MoS2 represents MoS2 nanospheres with a hollow structure, and the cavity diameter ranges from 70 to 380 nm. The preparation method of the nanoreactor includes the following steps: a) Weigh SiO2 nanospheres and 3-aminopropyltriethoxysilane and place them in a methanol solution and stir continuously until a uniform suspension is formed; after the suspension is completed, filter to obtain a solid and wash it several times with ethanol, and then dry to obtain amino-modified SiO2 nanospheres, i.e. N-SiO2. b) Add the above N-SiO2 to ethylene glycol and sonicate it to disperse it evenly; add deionized water and stir continuously until a uniform suspension is formed; then add ammonium tetrathiomolybdate and stir for 1-3 h; after the end, the solution is rotary evaporated and dried to obtain a reddish-brown powder; calcine the reddish-brown powder at 400-600 °C under a nitrogen atmosphere for 2-6 h to obtain MoS2 / N-SiO2; c) MoS2 / N-SiO2 was treated with 10-20 wt.% HF solution at room temperature for 12-24 h to etch away SiO2; after etching, the solid was separated, washed multiple times with water and anhydrous ethanol, and vacuum dried to obtain hollow MoS2 nanospheres. d) Weigh the above MoS2 and metal M salt and dissolve them in anhydrous ethanol. After stirring evenly, transfer the solution to a polytetrafluoroethylene hydrothermal reactor and react at 120-180 °C for 1-5 h. After the reaction is completed, allow it to cool naturally to room temperature, filter and separate to obtain a black solid. Wash it several times with deionized water and ethanol and then perform vacuum drying to obtain M / MoS2 loaded with metal M particles.

2. The application as described in claim 1, characterized in that, The diameter of the SiO2 nanospheres ranges from 70 to 380 nm, the concentration of SiO2 in the methanol solution is 0.03 to 0.045 g / mL, and the molar ratio of SiO2 to 3-aminopropyltriethoxysilane is 2:1 to 1:

2.

3. The application as described in claim 1, characterized in that, The concentration range of N-SiO2 in ethylene glycol is 0.4-1.2 g / mL, the volume ratio of ethylene glycol to deionized water is 1:20-1:10, and the mass ratio of N-SiO2 to ammonium tetrathiomolybdate is 2:1-1:

2.

4. The application as described in claim 1, characterized in that, The concentration of MoS2 in anhydrous ethanol is 1.25-2.5 mg / mL, and the metal M salt is one of nitrate, sulfate, or acetate.

5. The application as described in claim 1, characterized in that, Includes the following steps: 1) After thoroughly mixing the reaction substrate, hollow molybdenum disulfide nanoreactor, internal standard and reaction solvent, add them to the reaction vessel, seal it and replace the air in the vessel with hydrogen, and then fill the pressure in the vessel with hydrogen to the target pressure of 3 MPa~5 MPa. 2) Heat the reactor to 200 ℃~250 ℃ and start stirring. The reaction time is 3 h-6 h. 3) After the reaction is complete, stop stirring and cool to room temperature. Then, release the pressure and open the vessel to separate the liquid product and the nanoreactor. Use mass spectrometry-gas chromatography to perform qualitative and quantitative analysis on the liquid product and calculate the substrate conversion rate and aromatic product yield.

6. The application as described in claim 5, characterized in that, The reaction substrate is one of p-cresol, guaiacol, and diphenyl ether.

7. The application as described in claim 5, characterized in that, The mass ratio of the nanoreactor to the reaction substrate is 1:5 to 1:1; the reaction solvent is selected from n-pentane, n-hexane, and n-heptane.

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