Method of producing hierarchical porous beads
View Patent ↗The present invention is a method of producing porous beads, which comprises the steps of providing a first liquid phase comprising a bead matrix material and essentially edgy templating particle(s), said particle(s) being treated with a surface modifying agent; providing a second liquid phase which is immiscible with the first liquid phase; contacting the first phase and the second phase under conditions resulting in an emulsion of droplets comprised of the first liquid phase dispersed in the continuous second liquid phase; transforming the droplets to mesoporous beads by solidification of the liquid; and removing the templating particle(s) from the beads without causing any essential change of the surrounding bead, whereby hierarchical networks of pores are provided in the beads.
1. A method of producing at least one porous bead, which comprises the steps of
(a) providing a first liquid phase comprising a bead matrix material and at least one essentially edgy templating particle, said particle(s) being treated with a surface modifying agent;
(b) providing a second liquid phase which is immiscible with the first liquid phase;
(c) contacting the first phase and the second phase under conditions resulting in an emulsion of droplets comprised of the first liquid phase dispersed in the continuous second liquid phase;
(d) transforming the droplets to mesoporous beads by solidification of the liquid in said droplets; and
(e) removing the templating particle(s) from the beads without causing any essential change of the surrounding bead, whereby the mesoporous beads resulting from step (d) are supplemented with one or more larger pores corresponding to the cavities left by the removed templating particle(s);
whereby an essentially hierarchical network of pores is provided in each bead.
2. The method of claim 1 , wherein a surface modifying agent is present in the first liquid phase when the templating particle(s) are added therein.
3. The method of claim 1 , wherein the templating particle(s) are treated with a surface modifying agent before they are added to the first liquid phase.
4. The method of claim 1 , which further comprises a step of diluting the droplet phase before step (c).
5. The method of claim 1 , which further comprises a step of removing liquid from the droplet phase after step (c) but before step (d).
6. The method of claim 1 , wherein the concentration of the templating particle(s) in the droplet phase is close to the percolation threshold during the solidification.
7. The method of claim 1 , wherein the shape of the templating particle(s) is elongate and defined by an aspect ratio higher than two.
8. The method of claim 1 , wherein the shape of the templating particle(s) is edgy and defined by a sphericity lower than about 0.8.
9. The method of claim 1 , wherein the shape of the templating particle(s) is edgy and defined by a circularity of the particle projection(s) lower than about 0.85.
10. The method of claim 1 , wherein the templating particle(s) are acid-soluble and made from a material selected from the group consisting of carbonate minerals, oxide minerals, calcium phosphate, magnesium hydroxide, and metals.
11. The method of claim 10 , wherein the templating particles are removed by leaching with an acid.
12. The method of claim 1 , wherein the templating particle(s) are siliceous particles and made from a material selected from the group consisting of silica, diatomite, glass, and silicate minerals.
13. The method of claim 12 , wherein the templating particles are removed by leaching with a fluorine compound.
14. The method of claim 1 , wherein the templating particle(s) are organic or carbonaceous particles and made from a material selected from the group consisting of organic polymers, low molecular weight organic crystals and carbon.
15. The method of claim 1 , wherein the templating particle(s) are alkali-soluble particles and made from a material selected from the group consisting of siliceous particles, metal particles and oxides.
16. The method of claim 14 , wherein the templating particles are removed by leaching with a base.
17. The method of claim 1 , wherein the templating particles are volatilised by heat treatment, optionally in the presence of air or oxygen.
18. The method of claim 1 , wherein the droplet phase of the emulsion is comprised of oil droplets.
19. The method of claim 18 , wherein the bead matrix material is comprised of synthetic monomers and the transformation according to step (d) is a polymerisation in the presence of a porogen and a cross-linker.
20. The method of claim 1 , wherein the droplet phase of the emulsion is comprised of aqueous droplets.
21. The method of claim 20 , wherein the bead matrix material is comprised of a natural polymer and the transformation according to step (d) is a physical gelation.
22. The method of claim 20 , wherein the aqueous droplets comprise an inorganic compound and the transformation according to step (d) is a sol-gel precipitation.