Method for preparing organic hydrogenation catalyst based on noble metal nanoparticles

[0038] Example 1:

[0039] 1) Preparation of ~100nm silica balls: Add 15mL of ethyl orthosilicate (TEOS) to a mixed solution consisting of 294mL of ethanol, 24mL of deionized water and 7.5mL of aqueous ammonia (28wt%), and stir at room temperature for 12 hours, Centrifuge the silicon ball and redisperse it into 50 mL isopropanol (HPLC grade), then add 0.1 mL 3-amino-4-hydroxybenzene sulfonic acid (APS), reflux at 70°C for 10 hours, then centrifuge and use the solid part The mixture of anhydrous ethanol and water is cleaned and re-dispersed in 150ml of anhydrous ethanol to obtain a base dispersion after amino modification.

[0040] 2) Preparation of ultra-small platinum nanoparticle film layer on the surface of the silicon ball. Take 3mL of the amino-modified base dispersion prepared in step 1) and add it to a mixture of 20mL of absolute ethanol, 125mL of deionized water and 0.2mL of aqueous ammonia (28wt%), and add 0.3g of dodecyl Sodium benzene sulfonate (SDBS), stir evenly to obtain a base mixture. Mix resorcinol into a 25g/L solution, add K 2 PtCl 4 Prepare a 0.1mol/L solution. Take 10mL of the prepared resorcinol solution and 2mL K 2 PtCl 4 The solution was mixed with 0.42mL formaldehyde solution (37wt%) and added to the above-mentioned base mixture. After stirring for 24 hours in a water bath at 28°C, it was refluxed at 70°C for 10 hours, and then centrifuged. The solid part was composed of absolute ethanol and After the water mixture is washed several times, it is dried in an oven at 60°C, that is, a precious metal nanoparticle layer is prepared on the surface of the substrate, and an organic hydrogenation reaction catalyst based on precious metal nanoparticles is obtained.

[0041] figure 1 This is a transmission electron microscope picture of the ultra-small platinum nano-film layer on the surface of the silica sphere prepared in Example 1 of the present invention. figure 1 The medium and dark parts are platinum nanoparticles, the average particle size of platinum nanoparticles is 0.7nm, and the light parts are silica balls and the RF resin coating layer. The inset is a high-resolution transmission electron microscope picture in this example.

[0042] Example 2:

[0043] 1) Preparation of ~100nm silica balls: Add 15mL of ethyl orthosilicate (TEOS) to a mixed solution consisting of 294mL of ethanol, 24mL of deionized water and 7.5mL of aqueous ammonia (28wt%), and stir at room temperature for 12 hours, Centrifuge the silicon ball and redisperse it into 50 mL isopropanol (HPLC grade), then add 0.1 mL 3-amino-4-hydroxybenzene sulfonic acid (APS), reflux at 70°C for 10 hours, then centrifuge and use the solid part The mixture of anhydrous ethanol and water is cleaned and re-dispersed in 150ml of anhydrous ethanol to obtain a base dispersion after amino modification.

[0044] 2) Preparation of ultra-small platinum nanoparticle film layer on the surface of the silicon ball. Take 3mL of the amino-modified base dispersion prepared in step 1) and add it to a mixture of 20mL of absolute ethanol, 125mL of deionized water and 0.2mL of aqueous ammonia (28wt%), and add 0.3g of dodecyl Sodium benzene sulfonate (SDBS), stir evenly to obtain a base mixture. Mix resorcinol into a 25g/L solution, add K 2 PtCl 4 Prepare a 0.1mol/L solution. Take 10mL prepared resorcinol solution and 4mL K 2 PtCl 4 The solution was mixed with 0.42mL formaldehyde solution (37wt%) and added to the above-mentioned base mixture. After stirring for 24 hours in a water bath at 28°C, it was refluxed at 70°C for 10 hours, and then centrifuged. The solid part was composed of absolute ethanol and After the water mixture is washed several times, it is dried in an oven at 60°C, that is, a precious metal nanoparticle layer is prepared on the surface of the substrate to obtain an organic hydrogenation reaction catalyst based on precious metal nanoparticles.

[0045] figure 2 This is a transmission electron microscope picture of the ultra-small platinum nano-film layer on the surface of the silica sphere prepared in Example 2 of the present invention. figure 2 The medium and dark parts are platinum nanoparticles, the average particle size of platinum nanoparticles is 1.2nm, and the light parts are silica balls and the RF resin coating layer. The inset is a high-resolution transmission electron microscope picture in this example.

[0046] Example 3:

[0047] 1) Preparation of ~100nm silica balls: Add 15mL of ethyl orthosilicate (TEOS) to a mixed solution consisting of 294mL of ethanol, 24mL of deionized water and 7.5mL of aqueous ammonia (28wt%), and stir at room temperature for 12 hours, Centrifuge the silicon ball and redisperse it into 50 mL isopropanol (HPLC grade), then add 0.1 mL 3-amino-4-hydroxybenzene sulfonic acid (APS), reflux at 70°C for 10 hours, then centrifuge and use the solid part The mixture of anhydrous ethanol and water is cleaned and re-dispersed in 150ml of anhydrous ethanol to obtain a base dispersion after amino modification.

[0048] 2) Preparation of ultra-small platinum nanoparticle film layer on the surface of the silicon ball. Take 3mL of the amino-modified base dispersion prepared in step 1) and add it to a mixture of 20mL of absolute ethanol, 125mL of deionized water and 0.2mL of aqueous ammonia (28wt%), and add 0.3g of dodecyl Sodium benzene sulfonate (SDBS), stir evenly to obtain a base mixture. Mix resorcinol into a 25g/L solution, add K 2 PtCl 4 Prepare a 0.1mol/L solution. Take 10mL of the prepared resorcinol solution and 20mL K 2 PtCl 4 The solution was mixed with 0.42mL formaldehyde solution (37wt%) and added to the above-mentioned base mixture. After stirring for 24 hours in a water bath at 28°C, it was refluxed at 70°C for 10 hours, and then centrifuged. The solid part was composed of absolute ethanol and After washing the water mixture several times, it is dried in an oven at 60°C, that is, a precious metal nanoparticle layer is prepared on the surface of the substrate, and an organic hydrogenation reaction catalyst based on precious metal nanoparticles is obtained.

[0049] image 3 This is a transmission electron microscope picture of the ultra-small platinum nano-film layer on the surface of the silica sphere prepared in Example 3 of the present invention. image 3 The medium and dark parts are platinum nanoparticles, the average particle size of the platinum nanoparticles is 2.4nm, and the light parts are silica balls and the RF resin coating layer. The inset is a high-resolution transmission electron microscope picture in this example.