US5622684A — Porous inorganic oxide materials prepared by non-…

Claim 1

Independent Claim 64 words

A synthetic, semi-crystalline inorganic metal oxide composition having at least one resolved x-ray reflection corresponding to a lattice spacing of 3 to 10 nm, a framework wall thickness of at least about 2 nm, framework confined pores between about 2 and 10 nm, an elementary particle size greater than 500 nm, and a specific surface area of 300 to 1200 square meters per gram.

Claim 2

Dependent Claim 64 words

A synthetic, semi-crystalline inorganic metal oxide composition having at least one resolved x-ray reflection corresponding to a lattice spacing of 3 to 10 nm, a framework wall thickness of at least about 2 nm, framework confined pores between about 2 and 10 nm, an elementary particle size greater than 500 nm, and a specific surface area of 300 to 1200 square meters per gram.

Claim 3

Dependent Claim 20 words

The composition of claim 1 having an X-ray diffraction pattern selected from the group consisting of FIGS. 3 and 5.

Claim 4

Dependent Claim 26 words

The composition of claim 1 having an N 2 adsorption-desorption isotherms and Horvath-Kawazoe pore size distribution selected from the group consisting of FIGS. 4 and 6.

Claim 5

Dependent Claim 15 words

The composition of claim 1 having an X-ray diffraction pattern as shown in FIG. 7.

Claim 6

Dependent Claim 20 words

The composition of claim 1 having N 2 adsorption-desorption isotherms and Horvath-Kawazoe pore size distribution as shown in FIG. 8.

Claim 7

Dependent Claim 102 words

A synthetic, semi-crystalline inorganic metal oxide composition having at least one resolved x-ray reflection corresponding to a lattice spacing of 3 to 10 nm, a framework wall thickness of at least about 2 nm, framework confined pores between about 2 and 10 nm, an elementary particle size greater than 500 nm, and a specific surface area of 300 to 1200 square meters per gram prepared by reacting a mixture of a non-ionic poly(alkylene oxide) derived surfactant as a template (N°) and a neutral inorganic metal oxide precursor (I°), followed by hydrolysis and crosslinking of the inorganic oxide precursor to provide the composition.

Claim 8

Dependent Claim 102 words

A synthetic, semi-crystalline inorganic metal oxide composition having at least one resolved x-ray reflection corresponding to a lattice spacing of 3 to 10 nm, a framework wall thickness of at least about 2 nm, framework confined pores between about 2 and 10 nm, an elementary particle size greater than 500 nm, and a specific surface area of 300 to 1200 square meters per gram prepared by reacting a mixture of a non-ionic poly(alkylene oxide) derived surfactant as a template (N°) and a neutral inorganic metal oxide precursor (I°), followed by hydrolysis and crosslinking of the inorganic oxide precursor to provide the composition.

Claim 9

Dependent Claim 13 words

The composition of claim 6 wherein the template is removed from the composition.

Claim 10

Dependent Claim 13 words

The composition of claim 6 wherein the surfactant has a terminal hydroxyl group.

Claim 11

Dependent Claim 76 words

The composition of claim 6 which has the composition: nR--EO/A.sub.x O.sub.Y wherein R--EO is selected from the group consisting of nonionic alkyl polyethylene oxide, alkyl and aryl polyethylene oxide, and polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer molecules; A is a metal atom; O is oxygen and x and y are the molar stoichiometries of A, and O such that in the composition when calcined, n is about O, x is about 1, y is about 2.

Claim 12

Dependent Claim 140 words

The composition of claim 6 which has the composition: nR--EO/A.sub.v B.sub.w Si.sub.x D.sub.y O.sub.z wherein R--EO is selected from the group consisting of nonionic alkyl polyethylene oxide, alkyl and aryl polyethylene oxide and polyethylene oxide-polypropylene oxide-polyethylene oxide block co-polymer molecules; A is at least one optional trivalent element selected from the group consisting of Al, Ga and Fe; B is at least one optional tetravalent metallic element selected from the group consisting of Ge, Ti, V, Sb and Zr; Si is silicon; D is optional and is a pentavalent or hexavalent element selected from the group consisting of V, W and Mo; O is oxygen and v, w, x, y and z are the molar stoichiometries of A, B, Si, D and O respectively, wherein in the composition when calcined, n is about 0, ≦v≦2, 0≦w≦1, 0≦x≦1, 0≦y≦2 and 2≦z≦6.

Claim 13

Dependent Claim 25 words

The composition of claim 6 having X-ray diffraction patterns with at least one reflection corresponding to a lattice of between about 3 to 10 nm.

Claim 14

Dependent Claim 39 words

The composition of any one of claims 1 or which after calcination, has an N 2 , O 2 or Ar adsorption-desorption isotherm with a step at P/P O between 0.2 and 0.6 and at least one hysteresis loop.

Claim 15

Dependent Claim 29 words

The composition of claim 12 wherein a ratio of textural to framework-confined mesoporosity as determined by the N 2 , O 2 or Ar adsorption isotherm, is about zero.

Claim 16

Dependent Claim 20 words

The composition of claim 13 the composition has a specific surface area between 500 and 1200 m 2 per gram.

Claim 17

Dependent Claim 25 words

The composition of claim 6 wherein a molar ratio of nonionic surfactant to inorganic oxide precursor in the reaction mixture is between 0.05 and 0.2.

Claim 18

Dependent Claim 8 words

The composition of claim 6 containing the template.

Claim 19

Dependent Claim 14 words

The composition of claim 6 in which the template has been removed by calcination.

Claim 20

Dependent Claim 15 words

The composition of claim 6 in which the template has been removed through solvent extraction.

Claim 21

Dependent Claim 8 words

The composition of claim 6 containing the template.

Claim 22

Dependent Claim 14 words

The composition of claim 10 in which the template has been removed by calcination.

Claim 23

Dependent Claim 15 words

The composition of claim 10 in which the template has been removed through solvent extraction.

Claim 24

Dependent Claim 48 words

The composition of any one of claims 1 or 6 in which at least one transition metal is dispersed or impregnated in the pores, selected from the group consisting of Ag, Au, Cu, Co, Cr, Ni, Fe, Ir, Mo, Pt, Pd, Sn, Ti, V, W, Zn and Zr.

Claim 25

Dependent Claim 19 words

The composition of any one of claims 1 or 6 containing transition metal substituted organic macrocycles in the pores.

Claim 26

Dependent Claim 44 words

The composition of claim 6 wherein the surfaces of the composition have been functionalized by an alkyl metal alkoxide precursor represented as M--R(OR).sub.χ-1, where M is the metal, x represents available bonding sites on M and where R is alkyl and OR is alkoxide.

Claim 27

Dependent Claim 36 words

The composition of any one of claims 6 or 10 wherein the surfaces of the composition upon removal of the template have been functionalized by substitution of the metal alkoxide precursor by a metal carboxylate precursor.

Claim 28

Dependent Claim 45 words

The composition of any one of claims 1 or 6 wherein the compositions have surfaces which have been functionalized by reaction of the composition upon removal of the template and calcination with reagents selected from the group consisting of chlorides, fluorides, sylisation and alkylation reagents.

Claim 29

Dependent Claim 23 words

The composition of claim 6 wherein the template (N°) is selected from the group consisting of primary, secondary and tertiary fatty alcohol poly(ethoxylates).

Claim 30

Dependent Claim 15 words

The composition of claim 6 wherein the nonionic template (N°) is an alkyl phenol poly-(ethoxylates).

Claim 31

Dependent Claim 15 words

The composition of claim 6 wherein the nonionic template (N°) is a fatty acid ethoxylate.

Claim 32

Dependent Claim 17 words

The composition of claim 6 wherein the nonionic template (N°) is a poly(ethylene oxide-propylene oxide) block co-polymer.

Claim 33

Dependent Claim 22 words

The composition of claim 6 wherein the template (N°) is selected from the group consisting of primary and secondary fatty amine poly(ethoxylate).

Claim 34

Dependent Claim 18 words

The composition of claim 6 wherein the template (N°) is a fatty acid poly(ethylene oxide-propylene oxide) block co-polymer.

Claim 35

Dependent Claim 21 words

The composition of claim 6 wherein the template (N°) is selected from the group consisting of fatty acid alkanolamides and ethoxylates.

Claim 36

Dependent Claim 21 words

The composition of claim 6 wherein the template (N°) is selected from the group consisting of sorbitan esters and sorbitan ethoxylates.

Claim 37

Dependent Claim 14 words

The composition of claim 6 wherein the template (N°) is a polyamine propoxylate ethoxylate.

Claim 38

Independent Claim 98 words

A method for the preparation of a synthetic semi-crystalline inorganic oxide composition which comprises: (a) forming a solution by providing a mixture of (i) a neutral inorganic oxide precursor (I°) containing at least one element selected from the group consisting of di-, tri-, tetra-, penta- and hexavalent elements and mixture thereof; (ii) a non-ionic poly(alkylene oxide) surfactant (S°) as a template; and (iii) a hydrolyzing agent; (b) mixing the solution to form a gel containing the composition; (c) separating at least some of the hydrolyzing agent and the surfactant from the gel; and (d) optionally calcining the composition.

Claim 39

Independent Claim 98 words

A method for the preparation of a synthetic semi-crystalline inorganic oxide composition which comprises: (a) forming a solution by providing a mixture of (i) a neutral inorganic oxide precursor (I°) containing at least one element selected from the group consisting of di-, tri-, tetra-, penta- and hexavalent elements and mixture thereof; (ii) a non-ionic poly(alkylene oxide) surfactant (S°) as a template; and (iii) a hydrolyzing agent; (b) mixing the solution to form a gel containing the composition; (c) separating at least some of the hydrolyzing agent and the surfactant from the gel; and (d) optionally calcining the composition.

Claim 40

Dependent Claim 25 words

The method of claim 36 wherein the gel is prepared by a random order of addition of the neutral template and neutral inorganic oxide precursor.

Claim 41

Independent Claim 153 words

A method for the preparation of a synthetic, semi-crystalline inorganic oxide composition which comprises: (a) preparing a solution of a neutral inorganic oxide precursor (I°), containing at least one element selected from the group consisting of di-, tri-, tetra-, penta- and hexavalent elements and mixtures thereof with stirring and optionally aging the inorganic oxide precursor (I°) solution; (b) preparing a homogeneous solution of a nonionic poly(alkylene oxide) surfactant (S°) as a template in a hydrolyzing agent, and optionally in a co-solvent, by stirring it at a temperature between about minus 20° and plus 100° C; (c) mixing of the solutions of steps (a) and (b) at a temperature between about minus 20° and plus 100° C to form a gel which is aged for at least about 30 minutes to form the composition; (d) separating at least some of the hydrolyzing agent and surfactant from the composition; and (e) optionally calcining the composition.

Claim 42

Independent Claim 153 words

A method for the preparation of a synthetic, semi-crystalline inorganic oxide composition which comprises: (a) preparing a solution of a neutral inorganic oxide precursor (I°), containing at least one element selected from the group consisting of di-, tri-, tetra-, penta- and hexavalent elements and mixtures thereof with stirring and optionally aging the inorganic oxide precursor (I°) solution; (b) preparing a homogeneous solution of a nonionic poly(alkylene oxide) surfactant (S°) as a template in a hydrolyzing agent, and optionally in a co-solvent, by stirring it at a temperature between about minus 20° and plus 100° C; (c) mixing of the solutions of steps (a) and (b) at a temperature between about minus 20° and plus 100° C to form a gel which is aged for at least about 30 minutes to form the composition; (d) separating at least some of the hydrolyzing agent and surfactant from the composition; and (e) optionally calcining the composition.

Claim 43

Dependent Claim 34 words

The method of claim 38 wherein the neutral precursor is selected from the group consisting of a metal alkoxide, an inorganic complex, a colloidal inorganic oxide solution, an inorganic oxide sol and mixtures thereof.

Claim 44

Dependent Claim 15 words

The method of claim 38 wherein said inorganic oxide precursor solution is mixed without aging.

Claim 45

Dependent Claim 22 words

The method of claim 38 wherein the template is separated from the composition and as an additional step recycled after step (d).

Claim 46

Dependent Claim 29 words

The method of claim 41 wherein the template is separated by extraction with a solvent selected from the group consisting of a neutral organic solvent, water and mixtures thereof.

Claim 47

Dependent Claim 31 words

The method of claim 38 wherein in step (a) the solution is a gel with the stirring at a temperature of at least minus 20° C for at least 5 minutes.

Claim 48

Dependent Claim 22 words

The method of claim 38 wherein the composition is calcined at about 300° to 1000° C. for at least about 30 minutes.

Claim 49

Independent Claim 166 words

A method for the preparation of a crystalline inorganic oxide composition which comprises: (a) preparing a homogeneous solution of nonionic poly(ethylene oxide) surfactant as a template (N°) in a lower alkyl alcohol solvent by mixing at ambient temperature; (b) adding an inorganic metal precursor to the solution of step (a) at ambient temperature under stirring for at least 30 minutes to form a homogeneous solution; (c) slowly adding a solution of a hydrolyzing agent to the homogeneous solution to form a gel as a first precipitate in the aqueous solution; (d) aging of the first precipitate with stirring; (e) redispersion of the first precipitate in a lower alkyl alcohol; (f) aging the redispersion under stirring at ambient temperature for 16 to 48 hours to form a second precipitate; (g) separating the aqueous solution, lower alkanol and at least some of the template from the second precipitate by washing once with ethanol; and (h) drying the second precipitate in air at ambient temperature to form the composition.

Claim 50

Independent Claim 166 words

A method for the preparation of a crystalline inorganic oxide composition which comprises: (a) preparing a homogeneous solution of nonionic poly(ethylene oxide) surfactant as a template (N°) in a lower alkyl alcohol solvent by mixing at ambient temperature; (b) adding an inorganic metal precursor to the solution of step (a) at ambient temperature under stirring for at least 30 minutes to form a homogeneous solution; (c) slowly adding a solution of a hydrolyzing agent to the homogeneous solution to form a gel as a first precipitate in the aqueous solution; (d) aging of the first precipitate with stirring; (e) redispersion of the first precipitate in a lower alkyl alcohol; (f) aging the redispersion under stirring at ambient temperature for 16 to 48 hours to form a second precipitate; (g) separating the aqueous solution, lower alkanol and at least some of the template from the second precipitate by washing once with ethanol; and (h) drying the second precipitate in air at ambient temperature to form the composition.

Claim 51

Dependent Claim 13 words

The method of claim 45 wherein the calcining is by combustion in air.

Claim 52

Dependent Claim 24 words

The method of claim 45 wherein optionally heat treating the second precipitate to at least 373° K. in air for at least 16 hours.

Claim 53

Dependent Claim 16 words

The method of claim 45 wherein after step (h) the template is removed by solvent extraction.

Claim 54

Dependent Claim 28 words

The method of claim 45 wherein after step (h) the second precipitate is calcined between about 673° K. and 923° K. in air for at least 4 hours.

Claim 55

Independent Claim 165 words

A method for the preparation of synthetic, semi-crystalline inorganic silicon dioxide composition which comprises: (a) preparing a homogeneous aqueous solution of a nonionic poly(ethylene oxide) derived surfactant template (N°) with mixing at ambient temperature; (b) adding an inorganic silica precursor to the solution of step (a) at ambient temperature with stirring to form a solid, precipitate; (c) aging of the precipitate with stirring at ambient temperature for between 16 and 48 hours; (d) separating the aqueous solution and template from the precipitate followed by washing once with deionized water; (e) drying the precipitated and separated precipitate in air at ambient temperature; (f) heat treating the air dried precipitate in air at least 373° K. for at least 16 hours; (g) optionally removing any remaining template by solvent extraction from the heat treated precipitate; and (h) calcining the precipitate to remove any remaining template to cross-link the framework at between 673° K. and 923° K. in air for at least 4 hours to form the composition.

Claim 56

Independent Claim 165 words

A method for the preparation of synthetic, semi-crystalline inorganic silicon dioxide composition which comprises: (a) preparing a homogeneous aqueous solution of a nonionic poly(ethylene oxide) derived surfactant template (N°) with mixing at ambient temperature; (b) adding an inorganic silica precursor to the solution of step (a) at ambient temperature with stirring to form a solid, precipitate; (c) aging of the precipitate with stirring at ambient temperature for between 16 and 48 hours; (d) separating the aqueous solution and template from the precipitate followed by washing once with deionized water; (e) drying the precipitated and separated precipitate in air at ambient temperature; (f) heat treating the air dried precipitate in air at least 373° K. for at least 16 hours; (g) optionally removing any remaining template by solvent extraction from the heat treated precipitate; and (h) calcining the precipitate to remove any remaining template to cross-link the framework at between 673° K. and 923° K. in air for at least 4 hours to form the composition.

Claim 57

Dependent Claim 13 words

The method of claim 50 wherein the calcining is by combustion in air.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	2000-04-21	2000-10-21	2001-04-22	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	2004-04-21	2004-10-21	2005-04-22	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2008-04-21	2008-10-21	2009-04-22	$7700.00	Window Closed / Lapsed

Porous inorganic oxide materials prepared by non-ionic surfactant templating route

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