Selectively functionalized porous material

Patent metadata

Field	Value
Publication number	US-2017106362-A1
Application number	US-201514885514-A
Country	US
Kind code	A1
Filing date	Oct 16, 2015
Priority date	Oct 16, 2015
Publication date	Apr 20, 2017
Grant date	—

Abstract

A porous substrate susceptible to one or both of hydroxylation and alkoxylation by a first protic solvent is exposed to a first relative pressure of the first protic solvent. The porous substrate includes a first plurality of pores having a first average pore diameter and a second plurality of pores having a second average pore diameter that is greater than the first average pore diameter. The first relative pressure is effective to one or both of hydroxylate or alkoxylate substantially only pores of the first average pore diameter to form a first modified porous substrate. The first modified porous substrate is reacted with a first functionalizing reagent that is effective to functionalize one or both of hydroxylated or alkoxylated surfaces, thereby functionalizing substantially only the first plurality of the pores, to form a first functionalized porous substrate.

First claim

What is claimed is:

1 . A method, comprising:
exposing a porous substrate susceptible to one or both of hydroxylation and alkoxylation by a first protic solvent to a first relative pressure of the first protic solvent, wherein the porous substrate comprises a first plurality of pores having a first average pore diameter and a second plurality of pores having a second average pore diameter that is greater than the first average pore diameter, wherein the first relative pressure is effective to one or both of hydroxylate or alkoxylate substantially only pores of the first average pore diameter to form a first modified porous substrate; and reacting the first modified porous substrate with a first functionalizing reagent that is effective to functionalize one or both of hydroxylated or alkoxylated surfaces, thereby functionalizing substantially only the first plurality of the pores, to form a first functionalized porous substrate.

2 . The method of claim 1 , wherein the first average pore diameter and the second average pore diameter are each less than about 20 nm.

3 . The method of claim 1 , wherein the porous substrate comprises a third plurality of pores having a third average pore diameter that is greater than the second average pore diameter.

4 . The method of claim 3 , wherein the first average pore diameter is less than about 2 nm, the second average pore diameter is from about 2 nm to about 20 nm, and the third average pore diameter is greater than about 20 nm.

5 . The method of claim 1 , wherein the protic solvent comprises one or more members selected from the group consisting of water, alcohols, acids, bases, any other solvent capable of donating a proton, and combinations of the foregoing.

6 . The method of claim 1 , wherein the first functionalizing reagent comprises one or more members selected from the group consisting of thiols, amines, alkoxides, epoxides, carboxylic acids, carboxylic esters, sulfonic acids, sulfonate esters, aldehydes, ketones, phosphines, halides, cyano alkyl, isocyanato alkyl, unsaturated alkyl, unsaturated cyclic alkyls, metal alkoxy, acyloxy, halogens, amino groups, groups capable of reacting with hydroxylated or alkoxylated metal oxide surfaces, and combinations of the foregoing.

7 . The method of claim 1 , wherein the porous substrate comprises one or more members selected from the group consisting of a porous oxide, a metal oxide, silica, ceramic, zeolite, porous carbon, and combinations of the foregoing.

8 . The method of claim 1 , further comprising:
exposing the first functionalized porous substrate to a second relative pressure of the first protic solvent that is higher than the first relative pressure, wherein the second relative pressure is effective to one or both of hydroxylate or alkoxylate substantially only pores of the second average pore diameter to form a second modified porous substrate; and reacting the second modified porous substrate with a second functionalizing reagent that is effective to functionalize one or both of hydroxylated or alkoxylated surfaces, thereby functionalizing substantially only the second plurality of pores, to form a second functionalized porous substrate.

9 . The method of claim 8 , further comprising:
exposing the second functionalized porous substrate to a third relative pressure of the first protic solvent that is higher than the second relative pressure, wherein the third relative pressure is effective to one or both of hydroxylate or alkoxylate substantially only pores of a third average pore diameter, wherein the porous substrate comprises a third plurality of pores having the third average pore diameter, to form a third modified porous substrate; and further reacting the third modified porous substrate with a third functionalizing reagent that is effective to functionalize one or both of hydroxylated or alkoxylated surfaces, thereby functionalizing substantially only the third plurality of pores, to form a third functionalized porous substrate.

10 . The method of claim 1 , further comprising:
exposing the first functionalized porous substrate to a second relative pressure of a second protic solvent, wherein the second relative pressure is effective to one or both of hydroxylate or alkoxylate substantially only pores of the second average pore diameter to form a second modified porous substrate; and further reacting the second modified porous substrate with a second functionalizing reagent that is effective to functionalize one or both of hydroxylated or alkoxylated surfaces, thereby functionalizing substantially only the second plurality of pores, to form a second functionalized porous substrate.

11 . The method of claim 10 , further comprising:
exposing the second functionalized porous substrate to a third relative pressure of a third protic solvent, wherein the third relative pressure is effective to one or both of hydroxylate or alkoxylate substantially only pores of a third average pore diameter, wherein the porous substrate comprises a third plurality of pores having the third average pore diameter, to form a third modified porous substrate; and further reacting the third modified porous substrate with a third functionalizing reagent that is effective to functionalize one or both of hydroxylated or alkoxylated surfaces, thereby functionalizing substantially only the third plurality of pores, to form a third functionalized porous substrate.

12 . An article comprising:
a functionalized porous substrate comprising a first plurality of pores having a first average pore diameter and a second plurality of pores having a second average pore diameter that is greater than the first average pore diameter, wherein substantially only the first plurality of pores is functionalized with a first predetermined functional group, and the second plurality of pores is substantially free of the first predetermined functional group.

13 . The article of claim 12 , wherein the first average pore diameter and the second average pore diameter are each less than about 20 nm.

14 . The article of claim 12 , wherein the second plurality of pores is substantially non-functionalized.

15 . The article of claim 12 , wherein substantially only the second plurality of pores is functionalized with a second predetermined functional group.

16 . The article of claim 15 , further comprising a third plurality of pores having a third average pore diameter that is greater than the second average pore diameter, wherein substantially only the third plurality of pores is functionalized with a third predetermined functional group.

17 . The article of claim 16 , wherein the first average pore diameter is less than about 2 nm, the second average pore diameter is from about 2 nm to about 20 nm, and the third average pore diameter is greater than about 20 nm.

18 . The article of claim 12 , wherein the porous substrate comprises one or more members selected from the group consisting of a porous oxide, a metal oxide, silica, ceramic, zeolite, porous carbon, and combinations of the foregoing.

19 . A method, comprising:
exposing a porous substrate susceptible to one or both of hydroxylation and alkoxylation by a first protic solvent to a first relative pressure of the first protic solvent, wherein the porous substrate comprises a first plurality of pores having a first average pore diameter and a second plurality of pores having a second average pore diameter that is greater than the first average pore diameter, wherein the first relative pressure is effective to

Assignees

• IBM

Inventors

• Dubois Geraud J
• Michel Bruno
• Ruch Patrick
• Saliba Sarmenio
• Volksen Willi

Classifications

• B01J21/08

  Silica · CPC title

• B01J35/1057

  Operations & Transport · mapped topic

• B01J35/1061 Primary

  Operations & Transport · mapped topic

• B01J35/647 Primary

  2-50 nm · CPC title

• B01J35/643

  less than 2 nm · CPC title