Method for preparing SBA-15 loaded metal or metallic oxide composite material

Abstract

The invention relates to a method for preparing a SBA-15 loaded metal or metallic oxide composite material and belongs to the technical field of preparation of a mesoporous silicon dioxide based composite material. In the method, mesopores SBA-15 are used as carriers. The method comprises the following steps of: dispersing the mesopores into a nonpolar solvent after heating or vacuumizing the mesopores SBA-15 to remove water; adding aqueous solution of a metal precursor into the nonpolar solvent under the condition of magnetic stirring, so that the metal precursor immerses into pore paths under the drive of the nonpolar solvent and is adsorbed on the inner surface of silicon dioxide; and carrying out filtering, drying, roasting or reduction processing to obtain the mesoporous silicon dioxide loaded metal or metallic oxide composite material. The method has various raw materials and mild reaction conditions. The prepared composite material has high specific surface area and high porosity. The loading capacity, the dispersity and the structure of metal or metallic oxide in the pore paths can be controlled. No precursor waste is generated. The method is simple to operate, has low requirements on equipment and is suitable for mass production.

Description

technical field

[0001] The invention belongs to a method for preparing a mesoporous silica-based composite material, in particular to a method for preparing nanowires or nanoparticles loaded with metal or metal oxide in the channels of mesoporous SBA-15. Background technique

[0002] Mesoporous silica is a kind of material assembled by using surfactant as a template, using chemical processes such as sol-gel (sol-gel), aging, etc., through electrostatic interactions and hydrogen bonds between organic and inorganic substances. An inorganic porous material with a pore size between 2 and 30 nm, a narrow pore size distribution and a regular pore structure.

[0003] The pore size distribution of SBA-15 mesoporous silica is in the range of 4.6-30nm. It has certain chemical and thermodynamic stability, regular channels, large specific surface area, internal surface can be modified, and its amorphous skeleton structure is easy to dope. , so it has received extensive attention in the...

Examples

Embodiment 1

[0019] figure 1 It is the HRTEM picture of SBA-15 in Example 1 of the present invention, with SBA-15 as the carrier and manganese nitrate as the precursor, SBA-15 is loaded with Mn 2 o 3 nanowire composites.

[0020] Take 0.4g of SBA-15 mesoporous silica and vacuumize at 120°C to remove water, then add 6mL of n-hexane into the mesoporous silica, stir magnetically, and add 0.5mL of 1.5mol / L Mn( NO 3 ) 2 The solution was stirred at room temperature for 4 hours, n-hexane was removed, and then dried at 80°C for 4 hours; heated to 600°C at a rate of 1°C / min under an oxygen atmosphere, kept at 600°C for 4 hours, and cooled to room temperature. The molar ratio of raw materials is as follows: SBA-15: n-hexane: Mn 2+ :H 2 O=1.0:6.9:0.11:4.2. Detected as Mn by XRD 2 o 3 / SBA-15 composite.

[0021] Prepared Mn 2 o 3 / SBA-15 composite materials such as figure 2 As shown, Mn 2 o 3 The nanowires are evenly distributed in the pores of SBA-15, with a pore diameter of 7.8nm and...

Embodiment 2

[0023] Using SBA-15 as the carrier and nickel nitrate as the precursor, the SBA-15 loaded NiO nanoparticle composite was obtained.

[0024] Take 0.4g of SBA-15 mesoporous silica and vacuumize at 120°C to remove water, then add 6mL of cyclohexane into the mesoporous silica, stir magnetically, and add 0.5mL of 2.5mol / L Ni under stirring (NO 3 ) 2 The solution was stirred at room temperature for 4 hours to remove cyclohexane, then dried at 80°C for 4 hours; heated to 450°C at a rate of 1°C / min under an oxygen atmosphere, kept at 450°C for 4 hours, and cooled to room temperature. The molar ratio of raw materials is as follows: SBA-15: cyclohexane: Ni 2+ :H 2 O=1.0:8.3:0.19:4.2. It is NiO / SBA-15 composite material detected by XRD.

[0025] Prepared NiO / SBA-15 composites such as image 3 As shown, the nanoparticles of NiO are uniformly distributed in the pores of SBA-15, the pore diameter is 7.7nm, and the specific surface area is 341.4m 2 / g, the pore volume is 0.69cm 3 / g....

Embodiment 3

[0027] Using SBA-15 as a carrier and silver nitrate as a precursor, the SBA-15 loaded Ag nanowire composite material was obtained.

[0028] Take 0.2g of SBA-15 mesoporous silica and heat at 120°C to remove water, then add 20mL of n-hexane into the mesoporous silica, stir magnetically, and add 0.3mL of 1.0mol / L AgNO under stirring 3 The solution was stirred at room temperature for 4 hours, n-hexane was removed, and then dried at 80°C for 4 hours; heated to 350°C at a rate of 2°C / min under an oxygen atmosphere, kept at 350°C for 2 hours, and cooled to room temperature. The molar ratio of raw materials is as follows: SBA-15: n-hexane: Ag + :H 2 O=1.0:46:0.09:5.0. It is Ag / SBA-15 composite material detected by XRD.

[0029] Prepared Ag / SBA-15 composites such as Figure 4 As shown, Ag nanowires are evenly distributed in the pores of SBA-15, with a pore diameter of 7.7nm and a specific surface area of ​​541.8m 2 / g, the pore volume is 0.91cm 3 / g.

technical field

[0001] The invention belongs to a method for preparing a mesoporous silica-based composite material, in particular to a method for preparing nanowires or nanoparticles loaded with metal or metal oxide in the channels of mesoporous SBA-15. Background technique

[0002] Mesoporous silica is a kind of material assembled by using surfactant as a template, using chemical processes such as sol-gel (sol-gel), aging, etc., through electrostatic interactions and hydrogen bonds between organic and inorganic substances. An inorganic porous material with a pore size between 2 and 30 nm, a narrow pore size distribution and a regular pore structure.

[0003] The pore size distribution of SBA-15 mesoporous silica is in the range of 4.6-30nm. It has certain chemical and thermodynamic stability, regular channels, large specific surface area, internal surface can be modified, and its amorphous skeleton structure is easy to dope. , so it has received extensive attention in the...

Examples

Embodiment 1

[0019] figure 1 It is the HRTEM picture of SBA-15 in Example 1 of the present invention, with SBA-15 as the carrier and manganese nitrate as the precursor, SBA-15 is loaded with Mn 2 o 3 nanowire composites.

[0020] Take 0.4g of SBA-15 mesoporous silica and vacuumize at 120°C to remove water, then add 6mL of n-hexane into the mesoporous silica, stir magnetically, and add 0.5mL of 1.5mol / L Mn( NO 3 ) 2 The solution was stirred at room temperature for 4 hours, n-hexane was removed, and then dried at 80°C for 4 hours; heated to 600°C at a rate of 1°C / min under an oxygen atmosphere, kept at 600°C for 4 hours, and cooled to room temperature. The molar ratio of raw materials is as follows: SBA-15: n-hexane: Mn 2+ :H 2 O=1.0:6.9:0.11:4.2. Detected as Mn by XRD 2 o 3 / SBA-15 composite.

[0021] Prepared Mn 2 o 3 / SBA-15 composite materials such as figure 2 As shown, Mn 2 o 3 The nanowires are evenly distributed in the pores of SBA-15, with a pore diameter of 7.8nm and...

Embodiment 2

[0023] Using SBA-15 as the carrier and nickel nitrate as the precursor, the SBA-15 loaded NiO nanoparticle composite was obtained.

[0024] Take 0.4g of SBA-15 mesoporous silica and vacuumize at 120°C to remove water, then add 6mL of cyclohexane into the mesoporous silica, stir magnetically, and add 0.5mL of 2.5mol / L Ni under stirring (NO 3 ) 2 The solution was stirred at room temperature for 4 hours to remove cyclohexane, then dried at 80°C for 4 hours; heated to 450°C at a rate of 1°C / min under an oxygen atmosphere, kept at 450°C for 4 hours, and cooled to room temperature. The molar ratio of raw materials is as follows: SBA-15: cyclohexane: Ni 2+ :H 2 O=1.0:8.3:0.19:4.2. It is NiO / SBA-15 composite material detected by XRD.

[0025] Prepared NiO / SBA-15 composites such as image 3 As shown, the nanoparticles of NiO are uniformly distributed in the pores of SBA-15, the pore diameter is 7.7nm, and the specific surface area is 341.4m 2 / g, the pore volume is 0.69cm 3 / g....

Embodiment 3

[0027] Using SBA-15 as a carrier and silver nitrate as a precursor, the SBA-15 loaded Ag nanowire composite material was obtained.

[0028] Take 0.2g of SBA-15 mesoporous silica and heat at 120°C to remove water, then add 20mL of n-hexane into the mesoporous silica, stir magnetically, and add 0.3mL of 1.0mol / L AgNO under stirring 3 The solution was stirred at room temperature for 4 hours, n-hexane was removed, and then dried at 80°C for 4 hours; heated to 350°C at a rate of 2°C / min under an oxygen atmosphere, kept at 350°C for 2 hours, and cooled to room temperature. The molar ratio of raw materials is as follows: SBA-15: n-hexane: Ag + :H 2 O=1.0:46:0.09:5.0. It is Ag / SBA-15 composite material detected by XRD.

[0029] Prepared Ag / SBA-15 composites such as Figure 4 As shown, Ag nanowires are evenly distributed in the pores of SBA-15, with a pore diameter of 7.7nm and a specific surface area of ​​541.8m 2 / g, the pore volume is 0.91cm 3 / g.

Images