Siliceous materials having tunable porosity and surface morphology and methods of synthesizing same
View Patent ↗Non-spherical siliceous particles having a plurality of porous branches are disclosed and claimed. The porous branches are randomly oriented and elongated, ring-like, and/or aggregated. An additive introduced during synthesis of the particles modifies pore volume and morphology. The tunability of the pore volume includes an inner diameter ranging from about 2 Å to about 50,000 Å. Synthesizing the particles includes mixing under constant or intermittent stirring in a reaction vessel an aqueous silicic acid solution with an acidic heel solution to form a mixture. The stirring may optionally be performed at a variable speed. An additive is introduced into the mixture at a controlled rate, wherein the additive imposes a pH change from a lower pH to a higher pH to the mixture to induce siliceous particle precipitation. Optionally, a metal dopand may be introduced into the particles and/or at least a portion of an outer surface located outside of the pores and/or an inner surface located inside of the pores may be modified.
1. A method of synthesizing a particle, the method comprising:
(a) mixing under constant or intermittent stifling in a reaction vessel an aqueous silicic acid solution with an acidic solution to form a mixture, said stirring being optionally variable speed;
(b) introducing at a controlled rate an additive into the mixture, wherein the additive imposes a confined pH change from a lower pH to a higher pH to the mixture to induce siliceous particle precipitation;
(c) optionally introducing a solution containing a salt of a metal into the mixture; and
(d) optionally modifying at least a portion of an outer surface located outside of the pores and/or a at least a portion of an inner surface located inside of the pores;
thereby creating a particle that is non-spherical and siliceous, the particle further comprising a plurality of branches, each branch being randomly oriented and elongated, ring-like, and/or aggregated; a plurality of pores present in each branch, wherein a subset of the pores are interconnected; a tunable pore volume controlled by an additive introduced during synthesis of said particle; and a pore inner diameter ranging from about 2 Å to about 50,000 Å.
2. The method of claim 1 , wherein each branch has an outer diameter from about 3 nm to about 120 nm.
3. The method of claim 1 , wherein the tunable pore volume is tunable from about 0.10 cc/gram to about 2.5 cc/gram, based on nitrogen physisorption.
4. The method of claim 1 , wherein the additive is selected from the group consisting of: inorganic bases, organic bases, fluoride ion sources, surfactants, and combinations thereof.
5. The method of claim 1 , wherein at least a portion of an outer surface located outside of the pores is modified and/or at least a portion of an inner surface located inside of the pores is modified.
6. The method of claim 1 , including introducing at the controlled rate the additive using a technique selected from the group consisting of: addition at a constant unchanging rate; drop-wise addition; increasing/decreasing the addition rate in a step-wise fashion; increasing/decreasing the addition rate in a ramped fashion.
7. The method of claim 1 , wherein the metal in the solution containing the salt of the metal is selected from the group consisting of: transition metals; heavy metals; noble metals; rare earth metals; and combinations thereof.
8. The method of claim 1 , including exposing a solution of sodium silicate in the range of about 0.5 wt % to 13 wt % to an ion exchange resin to prepare the aqueous silicic acid solution.
9. The method of claim 1 , wherein the additive is selected from the group consisting of: organic acids, inorganic acids, fluoride ion sources, and combinations thereof.
10. The method of claim 1 , including imposing a pH change from an initial pH in the range of about 0 to 1.5 to a raised pH in the range of about 6 to 11.
11. The method of claim 1 , including introducing an acid solution into the reaction vessel if the pH rises above an ideal pH.
12. The method of claim 1 , wherein the reaction vessel includes a temperature control means.
13. The method of claim 1 , including drying the particle at a temperature from room temperature to about 300° C. and/or calcining said particles at a temperature from about 300° C. to about 1,200° C.