Process for preparation of mesoporous silica and organosilica materials

Patent metadata

Field	Value
Publication number	US-9296618-B2
Application number	US-201214115663-A
Country	US
Kind code	B2
Filing date	May 11, 2012
Priority date	Mar 31, 2011
Publication date	Mar 29, 2016
Grant date	Mar 29, 2016

Abstract

In this invention, we disclose a method as well as silica and/or organosilica mesoporous materials obtained by templating using nanocrystalline cellulose and removal of the latter using acidic conditions. The resultant mesoporous silica materials are characterized by having high surface area with tunable iridescence resulting from the long-range chiral nematic organization. This invention is an improvement over the formation of composite materials formed with nanocrystalline cellulose (NCC) and silica, where the calcination of the materials led to removal of the cellulose and formation of a mesoporous silica material. Characteristically, the removal of the NCC template using acidic conditions differentiates the silica materials thus obtained in two ways: (1) It does not lead to as significant contraction of the materials as from calcination thereby giving access to materials with larger mesopores; and (2) it allows the formation of mesoporous chiral nematic compositions that include heat-sensitive components. This approach may be used to prepare the first example of a mesoporous organosilica material with a chiral nematic pore structure. Examples of possible applications of this material include optical filters, adsorbents, chiral stationary phases for chromatography, sensors, composite materials, membranes, and templates for creating other chiral materials.

First claim

The invention claimed is:

1. A process of producing a mesoporous siliceous material having chiral nematic order comprising:
acid hydrolysis of cellulose in a siliceous composite selected from the group consisting of silica/nanocrystalline cellulose composites and organosilica/nanocrystalline cellulose composites to produce a mesoporous siliceous material having chiral nematic order from which nanocrystalline cellulose has been removed by said acid hydrolysis.

2. A process according to claim 1 , wherein said acid hydrolysis is carried out with a concentrated inorganic acid in water at a temperature of 70° C. to 120° C.

3. A process according to claim 2 , wherein said concentrated acid is hydrochloric acid, sulphuric acid, nitric acid or trifluoromethanesulfonic acid; and said concentrated acid is greater than 3M.

4. A process according to claim 3 , wherein said concentrated acid is hydrochloric acid at a concentration of 10 to 12M; and said temperature is >80° C.

5. A process according to claim 3 , wherein said concentrated acid is sulphuric acid at concentration of 4M to 8M.

6. A process according to claim 1 , including a step of removing residual cellulose and products of cellulose hydrolysis from said mesoporous siliceous material, after said acid hydrolysis, by oxidising said residual cellulose and products of cellulose hydrolysis.

7. A process according to claim 1 , wherein said hydrolysis is carried out with maintenance of pores of a volume corresponding to the volume of the composite occupied by the nanocrystalline cellulose (NCC).

8. A process according to claim 1 , wherein said composite comprises a siliceous matrix surrounding a skeleton of NCC crystals said crystals, said skeleton having chiral nematic order and occupying a volume in the composite defining potential mesopores and said chiral nematic order is retained by said mesopores.

9. A process according to claim 1 , wherein said siliceous composite is a silica/nanocrystalline cellulose composite having chiral nematic order and said mesoporous siliceous material is mesoporous silica having chiral nematic order.

10. A process according to claim 1 , wherein said siliceous composite is an organosilica/nanocrystalline cellulose composite and said mesoporous siliceous material is mesoporous organosilica.

11. A process according to claim 1 , wherein said mesoporous siliceous material is a free-standing film.

12. A process according to claim 1 , wherein said mesoporous siliceous material has mesopores with a peak pore diameter of at least 5nm.

Assignees

• Maclachlan Mark John
• Shopsowitz Kevin Eric
• Hamad Wadood Yasser
• Fpinnovations

Inventors

• Maclachlan Mark John
• Shopsowitz Kevin Eric
• Hamad Wadood Yasser

Classifications

• C01B33/126 Primary

  Preparation of silica of undetermined type · CPC title

• B01J20/24

  Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives · CPC title

• C01P2006/16

  Pore diameter · CPC title

• B01J20/3078

  Thermal treatment, e.g. calcining or pyrolizing · CPC title

• C09K19/3819

  Polysaccharides or derivatives thereof · CPC title