Hollow silicon nanocapsule supported catalyst, preparation method and application thereof

Abstract

The application discloses a kind of catalyst based on hollow silicon nanocapsule load and its preparation method, application, it is related to catalytic agent and organic synthesis field.Catalyst based on hollow silicon nanocapsule load preparation method includes: copper, palladium is loaded to carbon nanospheres, and intermediate is formed;Intermediate, CTAB, catalyst, tetraethyl silicate are mixed hydrolysis, calcine under inert atmosphere, 350~450 DEG C 1~4h, calcine in oxygen-containing atmosphere, 350~450 DEG C 2~8h, and catalyst based on hollow silicon nanocapsule load finished product is obtained.The catalyst of the application has large reaction area, and is active, can reduce the reaction temperature of morpholine or piperidine substitution reaction in the preparation process of aryl alpha ketone photoinitiator, and improve product yield.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst and organic synthesis, in particular to a kind of catalyst based on hollow silicon nanocapsule load and its preparation method, application. BACKGROUND

[0002] The aryl alpha ketone photoinitiator mainly includes photoinitiator 369, photoinitiator 379 and photoinitiator 389, and its specific structural formula is as follows:

[0003]

[0004] The main synthesis route of the aryl alpha ketone photoinitiator at present is to take fluorobenzene as starting material, obtain 4-fluorobutyrophenone under the catalysis of anhydrous aluminum chloride, then obtain bromide through bromination, obtain amino substitution product through dimethylamine amination of bromide, obtain quaternary ammonium salt through the reaction of amino substitution product and chlorobenzene, obtain rearrangement compound through catalytic rearrangement of quaternary ammonium salt under alkaline condition, and obtain 369 / 379 / 389 photoinitiator through substitution reaction of rearrangement compound and morpholine, but the reaction condition is harsh in morpholine substitution process, and the yield is low. SUMMARY

[0005] The technical problem to be solved by the present application is to provide a kind of catalyst based on hollow silicon nanocapsule load and its preparation method, which can effectively reduce the preparation temperature and pressure of aryl alpha ketone photoinitiator, improve the yield, and not produce fluorine-containing wastewater.

[0006] The technical problem to be solved by the present application is to provide a kind of catalyst based on hollow silicon nanocapsule load and its preparation method, which can effectively reduce the preparation temperature and pressure of aryl alpha ketone photoinitiator, improve the yield, and not produce fluorine-containing wastewater.

[0007] In order to solve the above technical problems, the present application provides a kind of preparation method of catalyst based on hollow silicon nanocapsule load, which comprises the following steps:

[0008] (1) provide or prepare carbon nanospheres;

[0009] (2) disperse carbon nanospheres in water to obtain dispersion A with a concentration of 1-5 g / L; disperse copper chloride in dispersion A to obtain dispersion B with a concentration of 3-10 g / L; mix dispersion A and dispersion B uniformly, and then solid-liquid separation to obtain intermediate A; wherein dispersion A is sulfuric acid solution, hydrochloric acid solution or nitric acid solution;

[0010] (3) disperse intermediate A in water to obtain dispersion C with a concentration of 5-12 g / L, then add divalent palladium salt solution and sodium acetate solution in sequence, mix for 3-8 h, and then solid-liquid separation to obtain intermediate B; wherein the Pd 2+The concentration of the divalent palladium salt solution is 0.03-0.2 mol / L, the concentration of the sodium acetate solution is 0.1-0.5 mol / L; the volume ratio of the divalent palladium salt solution to the dispersion liquid C is 0.1:10-0.3:10, and the volume ratio of the sodium acetate solution to the dispersion liquid C is 0.2:1-0.5:1;

[0011] (4) The intermediate B, a dispersant B, CTAB and a catalytic base are uniformly mixed to obtain a dispersion liquid D; wherein the dispersant B is one or more of water, ethanol or methanol, the catalytic base is selected from NaOH or NH3·H2O, the concentration of the intermediate B in the dispersion liquid D is 2-10 g / L, the concentration of CTAB is 1-3 g / L, and the concentration of the catalytic base is 0.5-2 mol / L;

[0012] (5) Tetraethyl silicate is added to the dispersion liquid D, and after stirring at 20-40℃ for 2-12 h, solid-liquid separation is performed to obtain an intermediate C; wherein the volume ratio of the dispersion liquid D to the tetraethyl silicate is 400:1-550:1;

[0013] (6) The intermediate C is calcined in an inert atmosphere at 350-450℃ for 1-4 h, and then calcined in an oxygen-containing atmosphere at 350-450℃ for 2-8 h to obtain a catalyst product based on hollow silicon nanocapsule loading.

[0014] As an improvement of the above technical solution, in step (6), the inert atmosphere is an inert gas atmosphere or a nitrogen atmosphere;

[0015] The oxygen-containing atmosphere is an oxygen atmosphere or an air atmosphere.

[0016] As an improvement of the above technical solution, in step (6), the intermediate is calcined in a nitrogen atmosphere at 390-420℃ for 1.5-2.2 h, and then calcined in an air atmosphere at 350-380℃ for 5-7 h to obtain a catalyst product based on hollow silicon nanocapsule loading.

[0017] As an improvement of the above technical solution, in step (1), glucose is dispersed in water to obtain a dispersion liquid E with a concentration of 120-150 g / L, and then hydrothermal reaction is performed at 200-300℃ for 2-5 h, and after solid-liquid separation, carbon nanospheres are obtained.

[0018] As an improvement of the above technical solution, in step (2), the dispersant A is a hydrochloric acid solution with a concentration of 0.01-0.1 mol / L.

[0019] As an improvement of the above technical solution, in step (3), the divalent palladium salt solution is a PdCl2 solution or a palladium acetate solution;

[0020] The concentration of Pd in the divalent palladium salt solution is 0.03-0.2 mol / L.2+ The concentration is 0.04–0.1 mol / L.

[0021] As an improvement to the above technical solution, in step (3), the divalent palladium salt solution is first added to the dispersion C and stirred at 20-40℃ for 3-8 hours. Then, sodium acetate solution is added and stirred at 20-40℃ for 5-10 minutes before solid-liquid separation to obtain intermediate B.

[0022] As an improvement to the above technical solution, in step (4), the dispersant B is a mixture of water and ethanol, and the volume ratio of water to ethanol is 1.5:1 to 3:1.

[0023] The catalytic base is selected from NH3·H2O.

[0024] Accordingly, the present invention also discloses a catalyst supported on hollow silicon nanocapsules, which is prepared by the above-described preparation method.

[0025] Accordingly, the present invention also discloses the application of the above-mentioned catalyst supported on hollow silicon nanocapsules in the preparation of aryl α-ketone photoinitiators.

[0026] Implementing this invention has the following beneficial effects:

[0027] The catalyst based on hollow silicon nanocapsules of the present invention first uses carbon nanospheres to load copper chloride and divalent palladium salt, then reduces them to form palladium-carbon nanoparticles. The palladium-carbon nanoparticles are then mixed with TEOS, templates, etc., and calcined under a specific atmosphere after hydrolysis and polycondensation to obtain the catalyst supported on hollow silicon nanocapsules. This catalyst has a large reaction area and strong activity, and can effectively optimize the preparation process of aryl α-ketone photoinitiators, including the reaction conditions of morpholine substitution reactions (reducing temperature, pressure, etc.), while effectively improving the yield of photoinitiator products. Attached Figure Description

[0028] Fig. 1 This is a scanning electron microscope image of the carbon nanoparticles in Example 2;

[0029] Fig. 2 This is a scanning electron microscope image of palladium nanoparticles on carbon in Example 2;

[0030] Fig. 3 This is a scanning electron microscope image of the catalyst product from Example 2. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0032] This invention discloses a method for preparing a catalyst supported on hollow silicon nanocapsules, which includes the following steps:

[0033] (1) providing or preparing carbon nanospheres;

[0034] The carbon nanospheres are solid carbon nanospheres with an average particle size of 150-300 nm. The carbon nanospheres with such a particle size can be effectively decomposed in a subsequent treatment process, thereby forming hollow and porous silicon nanocapsules and improving the reactivity. If the particle size is too small, the amount of loaded Pd metal and Cu metal is too small, and the reactivity is low. If the particle size is too large, the decomposition is not complete in the subsequent heat treatment process, the pore structure is small, and the reactivity is low. Preferably, the average particle size of the carbon nanospheres is 180-220 nm, and more preferably 190-205 nm.

[0035] Specifically, in an embodiment of the present application, the carbon nanospheres can be prepared by dispersing glucose in water to obtain a dispersion E with a concentration of 120-150 g / L, and then performing hydrothermal reaction at 200-300 °C for 2-5 h. After solid-liquid separation, the carbon nanospheres are obtained.

[0036] Preferably, the obtained product is rinsed with water and ethanol for 2-3 times, respectively, after solid-liquid separation, and then dried to obtain the carbon nanospheres.

[0037] (2) dispersing the carbon nanospheres in water to obtain a dispersion A; dispersing copper chloride in the dispersion A to obtain a dispersion B; and mixing the dispersion A and the dispersion B uniformly, and then performing solid-liquid separation to obtain an intermediate A;

[0038] The concentration of the carbon nanospheres in the dispersion A is 1-5 g / L, and examples include 1.5 g / L, 1.8 g / L, 2.2 g / L, 2.6 g / L, 3.1 g / L or 4.3 g / L, but are not limited thereto. Preferably, the concentration is 1-3 g / L, and more preferably 1.5-3 g / L.

[0039] The concentration of the copper chloride in the dispersion is 3-10 g / L, and examples include 3.4 g / L, 4.2 g / L, 5 g / L, 5.8 g / L, 6.6 g / L, 7.4 g / L, 8.2 g / L or 9.5 g / L, but are not limited thereto. Preferably, the concentration is 4-8 g / L, and more preferably 4-6 g / L.

[0040] The dispersion A is a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution, but is not limited thereto. The concentration of H + in the dispersion A is 0.01-0.2 mol / L, preferably 0.01-0.1 mol / L, and more preferably 0.01-0.05 mol / L. Preferably, in an embodiment of the present application, the dispersion A is a hydrochloric acid solution.

[0041] Specifically, the dispersion liquid A and the dispersion liquid B are mixed, and then continuously stirred at 20-40°C for 5-20 min, followed by solid-liquid separation, and the obtained precipitate is washed with water for 2-5 times to obtain the intermediate A.

[0042] (3) The intermediate A is dispersed in water to obtain a dispersion liquid C, and then a divalent palladium salt solution and a sodium acetate solution are sequentially added, and mixed for 3-8 h, followed by solid-liquid separation to obtain the intermediate B;

[0043] In the dispersion liquid C, the concentration of the intermediate A is 5-12 g / L, and is exemplarily 5.2 g / L, 6.4 g / L, 7 g / L, 8 g / L, 9.2 g / L, 10.3 g / L or 11.5 g / L, but is not limited thereto. Preferably, the concentration is 6-10 g / L, and more preferably, the concentration is 6-9 g / L.

[0044] The divalent palladium salt solution is exemplarily a PdCl2 aqueous solution or a palladium acetate aqueous solution, but is not limited thereto. The concentration of Pd2+ in the divalent palladium salt solution is 0.03-0.2 mol / L, and is exemplarily 0.04 mol / L, 0.08 mol / L, 0.11 mol / L, 0.15 mol / L or 0.18 mol / L, but is not limited thereto. Preferably, the concentration is 0.03-0.1 mol / L, and more preferably, the concentration is 0.03-0.08 mol / L. 2+

[0045] The volume ratio of the divalent palladium salt solution to the dispersion liquid C is 0.1:10-0.3:10, and is exemplarily 0.12:10, 0.15:10, 0.2:10, 0.23:10 or 0.25:10, but is not limited thereto.

[0046] The sodium acetate solution is exemplarily a sodium acetate aqueous solution, and the concentration of sodium acetate in the sodium acetate solution is 0.1-0.5 mol / L, and is exemplarily 0.12 mol / L, 0.17 mol / L, 0.22 mol / L, 0.3 mol / L, 0.34 mol / L, 0.42 mol / L or 0.48 mol / L, but is not limited thereto. Preferably, the concentration is 0.1-0.3 mol / L, and more preferably, the concentration is 0.15-0.3 mol / L.

[0047] The volume ratio of the sodium acetate solution to the dispersion liquid C is 0.2:1-0.5:1, and is exemplarily 0.23:1, 0.26:1, 0.3:1, 0.34:1, 0.38:1, 0.44:1 or 0.49:1, but is not limited thereto.

[0048] Preferably, in one embodiment of the present application, the divalent palladium salt solution is first added to the dispersion liquid C, and then stirred at 20-40°C for 3-8 h, followed by adding the sodium acetate solution, and then stirring and mixing at 20-40°C for 5-10 min, followed by solid-liquid separation, and then washing with water for 3-5 times, and then drying to obtain the intermediate B.​

[0049] (4) mixing intermediate B, dispersant B, CTAB and catalytic base uniformly to obtain dispersion D;

[0050] The dispersant B is one or more of water, ethanol or methanol, but is not limited thereto. Preferably, it is a mixture of water and ethanol, and the volume ratio of water to ethanol is 1.5:1 to 3:1.

[0051] The catalytic base is selected from NaOH or NH3·H2O, but is not limited thereto. Preferably, NH3·H2O is selected.

[0052] In the dispersion D, the concentration of the catalytic base is 0.5 to 2 mol / L; and an example is 0.8 mol / L, 1.1 mol / L, 1.4 mol / L or 1.7 mol / L, but is not limited thereto.

[0053] In the dispersion D, the concentration of intermediate B is 2 to 10 g / L; and an example is 2.5 g / L, 3.5 g / L, 5 g / L, 6.5 g / L, 8 g / L or 9 g / L, but is not limited thereto.

[0054] In the dispersion D, the concentration of CTAB is 1 to 3 g / L; and an example is 1.2 g / L, 1.5 g / L, 1.8 g / L, 2.2 g / L, 2.6 g / L or 2.9 g / L, but is not limited thereto.

[0055] (5) tetraethyl silicate is added to the dispersion D, and after stirring at 20°C to 40°C for 2 to 12 hours, solid-liquid separation is performed to obtain intermediate C;

[0056] The volume ratio of the dispersion D to the tetraethyl silicate is 400:1 to 550:1; and an example is 420:1, 440:1, 480:1, 510:1 or 520:1, but is not limited thereto. The tetraethyl silicate is hydrolyzed and polycondensed under the catalysis of the catalytic base, and the SiO2 nanoparticles formed are coated on the surface of the intermediate C.

[0057] Preferably, after the solid-liquid separation, the product is eluted with water and ethanol each for 3 times in sequence, to obtain the intermediate C.

[0058] (6) calcining the intermediate C at 350°C to 450°C for 1 to 4 hours in an inert atmosphere, and then calcining at 350°C to 450°C for 2 to 8 hours in an oxygen-containing atmosphere to obtain a finished product of a catalyst based on hollow silica nanocapsules.

[0059] The inert atmosphere can be an inert gas atmosphere or a nitrogen atmosphere, but is not limited thereto. Preferably, it is a nitrogen atmosphere. The calcination temperature in the inert atmosphere is preferably 390°C to 420°C, and the calcination time is preferably 1.5 to 2.2 hours.

[0060] The oxygen-containing atmosphere is not limited to oxygen or air, but preferably air. The preferred calcination temperature is 350-380℃, and the preferred calcination time is 5-7h.

[0061] After the above calcination, the average particle size of the obtained catalyst product is 180-250nm, and the catalyst product has a coating structure with multiple pores in the coating layer, which allows the reactants to enter the catalyst during the preparation of the aryl alpha-ketone photoinitiator, effectively reducing the reaction temperature and reaction pressure and improving the yield.

[0062] The application further discloses a hollow silicon nanocapsule-loaded catalyst prepared by the preparation method.

[0063] The application further discloses an application of the hollow silicon nanocapsule-loaded catalyst in the preparation of an aryl alpha-ketone photoinitiator. More specifically, in the preparation process of the aryl alpha-ketone photoinitiator, the step of substitution reaction using morpholine or piperidine (as shown in the following figure), the catalyst can control the reaction temperature of the step to be 60-70℃, and the reaction time to be 12-15h.

[0064]

[0065] The application is further explained below by means of specific examples:

[0066] Example 1

[0067] The application provides a hollow silicon nanocapsule-loaded catalyst, and a specific preparation method thereof is as follows:

[0068] Dissolve 20g of glucose in 150mL of water to form a clear solution, and then transfer the solution to a 200mL sealed hydrothermal kettle. Keep the temperature at 210℃ under high pressure for 4h. After cooling, centrifugal separation, washing with water and ethanol for three times, and drying in a 100℃ oven, carbon nanometer powder is obtained. Disperse 0.2g of the carbon nanometer ball in 100mL of distilled water, stir for 10min, and use as solution A. Dissolve 0.2g of copper chloride in 40mL of 0.02mol / L hydrochloric acid solution as solution B. Mix solution A and B and stir for 10min. Then centrifugal separation the suspension. After washing with distilled water for five times, disperse the precipitate in 50mL of distilled water. Add 750μL of 0.05mol / L PdCl2 aqueous solution. After stirring for 5h, add 20mL of 0.2mol / L sodium acetate aqueous solution. After centrifugal separation, wash with distilled water for five times, and dry at 80℃ for 12h to obtain palladium carbon nanometer powder.

[0069] The obtained palladium carbon nanometer powder was dispersed in a solution containing 50 mL of water, 25 mL of ethanol, 2 g / L of CTAB and 1 mol / L of NH3H2O at a concentration of 6 g / L, and was ultrasonically treated for 20 min. Then 0.15 mL of TEOS was added, and stirring was performed for 10 h. After centrifugation, the precipitate was washed with distilled water and ethanol for 3 times, and was dried at 80°C for 6 h. Then calcination was performed at 380°C under nitrogen protection for 2 h, and then calcination was performed at 420°C in air for 6 h.

[0070] Example 2

[0071] The present embodiment provides a catalyst based on hollow silicon nanometer capsule loading, and a specific preparation method is as follows:

[0072] Glucose 20 g was dissolved in 150 mL of water to form a clear solution, and then was transferred into a 200 mL sealed hydrothermal kettle. High temperature and high pressure were maintained at 210°C for 4 hours. After cooling, centrifugal separation was performed, and washing was performed with water and ethanol for 3 times. Drying was performed in a 100°C oven to obtain carbon nanometer powder. 0.2 g of the carbon nanometer ball was dispersed in 100 mL of distilled water, stirring was performed for 10 min, and then was used as solution A. 0.2 g of copper chloride was dissolved in 40 mL of 0.02 mol / L hydrochloric acid solution to be used as solution B. Solution A and B were mixed, and stirring was performed for 10 min. Then the suspension was centrifuged. After washing with distilled water for 5 times, the precipitate was dispersed in 50 mL of distilled water. 750 μL of 0.05 mol / L PdCl2 aqueous solution was added. After stirring for 5 h, 20 mL of 0.2 mol / L sodium acetate aqueous solution was added. After centrifugation, washing was performed with distilled water for 5 times, and drying was performed at 80°C for 12 h to obtain palladium carbon nanometer powder.

[0073] The obtained palladium carbon nanometer powder was dispersed in a solution containing 50 mL of water, 25 mL of ethanol, 2 g / L of CTAB and 1 mol / L of NH3H2O at a concentration of 6 g / L, and was ultrasonically treated for 20 min. Then 0.15 mL of TEOS was added, and stirring was performed for 10 h. After centrifugation, the precipitate was washed with distilled water and ethanol for 3 times, and was dried at 80°C for 6 h. Then calcination was performed at 380°C under nitrogen protection for 2 h, and then calcination was performed at 420°C in air for 6 h.

[0074] The carbon nanometer powder, palladium carbon nanometer powder and catalyst product in Example 2 were analyzed by scanning electron microscopy, and specific results are shown in Figs. 1-3 , wherein, Fig. 1 is a scanning electron microscope image of the carbon nanometer powder, and from Fig. 1 it can be seen that the carbon nanometer powder is in the form of a sphere with high uniformity, and the average particle size is about 200 nm; Fig. 2 is a scanning electron microscope image of the palladium carbon nanometer powder, and from Fig. 2It can be seen that some Pd, Cu is loaded on the periphery of the carbon nano-powder. Fig. 3 is a scanning electron microscope image of the catalyst product, from Fig. 3 It can be seen that a layer of material is attached to the outside of the spheres, which is porous SiO2.

[0075] Example 3

[0076] 4.1 g of 369 raw material (compound as shown in formula (I)) was added to 16 g of water, 1.8 g of potassium carbonate, 2.3 g of morpholine, and 0.04 g of nanometer catalyst (Example 2) was sequentially added to a reaction bottle, the reactor was sealed by nitrogen replacement, and the temperature was raised to 65°C for 12-13 hours. The raw material was detected by HPLC to be ≤0.5%. 100 ml of dichloromethane and 50 ml of water were added, and the catalyst was removed by stirring and filtration for reuse. The organic phase was washed with water twice, dried with anhydrous sodium sulfate, and concentrated to obtain 4.76 g of yellow solid with a purity of ≥89%. The solid was added to 20 ml of ethanol, and the temperature was raised to 70-80°C for 2 h to dissolve the solid. The temperature was gradually lowered to 3°C to precipitate the solid, and the solid was filtered to obtain 3.8 g of yellow solid with a purity of ≥98%.

[0077]

[0078] Example 4

[0079] 3.3 g of 379 raw material (compound as shown in formula (II)) was added to 14 g of water, 1.4 g of potassium carbonate, 1.8 g of morpholine, and 0.03 g of nanometer catalyst was sequentially added to a reaction bottle, the reactor was sealed by nitrogen replacement, and the temperature was raised to 70°C for 12-13 hours. The raw material was detected by HPLC to be ≤0.5%. 80 ml of dichloromethane and 30 ml of water were added, and the catalyst was removed by stirring and filtration for reuse. The organic phase was washed with water twice, dried with anhydrous sodium sulfate, and concentrated to obtain 3.9 g of yellow solid with a purity of ≥93%. The solid was added to 15 ml of ethanol, and the temperature was raised to 80°C for 2 h to dissolve the solid. The temperature was gradually lowered to 2°C to precipitate the solid, and the solid was filtered to obtain 3.5 g of yellow solid with a purity of ≥98%.

[0080]

[0081] Example 5

[0082] Into a reaction flask, 3.1 g of 389 raw material (a compound as shown in formula (I)) was added into 14 g of water, 1.4 g of potassium carbonate, 1.8 g of piperidine, and 0.04 g of nano catalyst (Example 2) was added in sequence, the reactor was sealed by nitrogen replacement, and was heated to 65 °C for 12-13 hours. The raw material was detected by HPLC to be less than or equal to 0.5%. Then, 80 ml of dichloromethane and 40 ml of water were added, the catalyst was removed by filtration, and the organic phase was washed twice with water, dried with anhydrous sodium sulfate, and concentrated to obtain 3.64 g of white solid with a purity of greater than or equal to 90%. The solid was added into 15 ml of ethanol, heated to 75 °C for 2 hours, and then cooled to 5 °C to precipitate the solid. The solid was filtered to obtain 3.3 g of white solid with a purity of greater than or equal to 98%.

[0083] The above describes the preferred embodiments of the application. It should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the application, and these improvements and refinements are also considered to be within the protection scope of the application.

Claims

1. Use of a catalyst supported on hollow silica nanocapsules for the preparation of aryl α-ketone photoinitiators, characterized in that, The preparation method of the catalyst based on hollow silicon nanocapsule loading comprises the following steps: (1) dispersing glucose in water to obtain a dispersion E with a concentration of 120-150 g / L, then hydrothermal reaction at 200-300 DEG C for 2-5h, solid-liquid separation to obtain carbon nanospheres; (2) dispersing the carbon nanospheres in water to obtain a dispersion A with a concentration of 1-5 g / L; dispersing copper chloride in the dispersion A to obtain a dispersion B with a concentration of 3-10 g / L; mixing the dispersion A and the dispersion B uniformly, then solid-liquid separation to obtain an intermediate A; wherein the dispersion A is a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution; (3) dispersing the intermediate A in water to obtain a dispersion liquid C with a concentration of 5-12 g / L, adding a divalent palladium salt solution and a sodium acetate solution in sequence, and separating the solid and liquid after mixing for 3-8 h to obtain an intermediate B; wherein the concentration of Pd in the divalent palladium salt solution is 0.03-0.2 mol / L, and the concentration of sodium acetate in the sodium acetate solution is 0.1-0.5 mol / L; the volume ratio of the divalent palladium salt solution to the dispersion liquid C is 0.1:10-0.3:10, and the volume ratio of the sodium acetate solution to the dispersion liquid C is 0.2:1-0.5:1; 2+ (3) dispersing the intermediate A in water to obtain a dispersion liquid C with a concentration of 5-12 g / L, adding a divalent palladium salt solution and a sodium acetate solution in sequence, and separating the solid and liquid after mixing for 3-8 h to obtain an intermediate B; wherein the concentration of Pd in the divalent palladium salt solution is 0.03-0.2 mol / L, and the concentration of sodium acetate in the sodium acetate solution is 0.1-0.5 mol / L; the volume ratio of the divalent palladium salt solution to the dispersion liquid C is 0.1:10-0.3:10, and the volume ratio of the sodium acetate solution to the dispersion liquid C is 0.2:1-0.5:1; (4) mixing the intermediate B, a dispersion B, CTAB and a catalytic base uniformly to obtain a dispersion D; wherein the dispersion B is one or more of water, ethanol or methanol, the catalytic base is selected from NaOH or NH3H2O, the concentration of the intermediate B in the dispersion D is 2-10 g / L, the concentration of CTAB is 1-3 g / L, and the concentration of the catalytic base is 0.5-2 mol / L; (5) adding tetraethyl silicate in the dispersion D, stirring at 20-40 DEG C for 2-12h, then solid-liquid separation to obtain an intermediate C; wherein the volume ratio of the dispersion D to the tetraethyl silicate is 400:1-550:1; (6) calcining the intermediate C in an inert atmosphere at 350-450 DEG C for 1-4h, then calcining in an oxygen-containing atmosphere at 350-450 DEG C for 2-8h to obtain a catalyst based on hollow silicon nanocapsule loading; The catalyst based on hollow silicon nanocapsule loading is used for preparing aryl alpha ketone photoinitiator.

2. Use according to claim 1, wherein In step (6), the inert atmosphere is an inert gas atmosphere or a nitrogen atmosphere; The oxygen-containing atmosphere is an oxygen atmosphere or an air atmosphere.

3. The use according to claim 1, wherein In step (6), the intermediate is calcined in a nitrogen atmosphere at 390-420 DEG C for 1.5-2.2h, then calcined in an air atmosphere at 350-380 DEG C for 5-7h to obtain a catalyst based on hollow silicon nanocapsule loading.

4. The use according to claim 1, wherein In step (1), the glucose is dispersed in water to obtain a dispersion E with a concentration of 120-150 g / L, then hydrothermal reaction at 200-300 DEG C for 2-5h, the obtained product is rinsed with water and ethanol for 2-3 times respectively after solid-liquid separation, and then dried to obtain carbon nanospheres.

5. The use according to claim 1, wherein In step (2), the dispersion A is a hydrochloric acid solution with a concentration of 0.01-0.1 mol / L.

6. The use according to claim 1, wherein In step (3), the divalent palladium salt solution is a PdCl2 solution or a palladium acetate solution; Pd in ​​the divalent palladium salt solution 2+ The concentration is 0.04~0.1mol / L.

7. The use according to claim 1, wherein the compound is ###00003### 1 In step (3), the divalent palladium salt solution is first added to the dispersion C, stirred at 20-40 DEG C for 3-8h, then a sodium acetate solution is added, stirred and mixed at 20-40 DEG C for 5-10 min, then solid-liquid separation to obtain the intermediate B.

8. The use according to claim 1, wherein In step (4), the dispersion B is selected from a mixture of water and ethanol, and the volume ratio of water to ethanol is 1.5:1-3:1; The catalytic base is selected from NH3H2O.

9. The use according to claim 1, wherein The aryl alpha ketone photoinitiator includes 369 initiator, 379 initiator or 389 initiator.

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