US5795559A
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US
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Porous inorganic oxide materials prepared by non-ionic surfactant templating route
Assignee: Michigan State University
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Filing: 1996-05-02
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Granted: 1998-08-18
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Expires: 2016-05-02
Abstract
Abstract A method for the preparation of new semi-crystalline, porous inorganic oxide compositions possessing uniform framework-confined mesopores in the range 2.0-10.0 nm. The method uses an interaction between various nonionic polyethylene oxide based surfactants (N DEG ) and neutral inorganic oxide precursors (I &squ& ) at ambient reaction temperatures. The materials formed exhibit a disordered assembly of worm-like channels of regular diameter owing to the specific mechanism of self-assembly, producing highly stable materials and particles incorporating large numbers of the channels. This (N DEG I DEG ) templating approach introduces several new concepts to mesostructure synthesis. The application of the low-cost, non-toxic and biodegradable surfactants and ambient reaction temperatures, introduces environmentally clean synthetic techniques to the formation of mesostructures. Recovery of the template can be achieved through solvent extraction where the solvent may be water or ethanol.
Inventors
- 👤 Thomas J. Pinnavaia
- 👤 Stephen A. Bagshaw
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 20:36
CPC Classifications
C; C01; C01B; C01B37/00; C01B37/02; C01B37/005; C01F; C01F7/00; C01F7/02; C01F7/34; C01F7/36; C01P; C01P2002/00; C01P2002/04; C01P2002/70; C01P2002/72; C01P2004/00; C01P2004/60; C01P2004/62; C01P2006/00; C01P2006/12; C01P2006/16
Claims Analysis
Total Claims: 57
Claim 1
Independent Claim
54 words
A synthetic, semi-crystalline inorganic oxide composition having at least one resolved x-ray reflection corresponding to a lattice spacing of 3 to 10 nm, framework confined channels between about 2 and 10 nm diameter, and a specific surface area of 300 to 1400 square meters per gram and having a disordered assembly of worm channels.
Claim 2
Dependent Claim
54 words
A synthetic, semi-crystalline inorganic oxide composition having at least one resolved x-ray reflection corresponding to a lattice spacing of 3 to 10 nm, framework confined channels between about 2 and 10 nm diameter, and a specific surface area of 300 to 1400 square meters per gram and having a disordered assembly of worm channels.
Claim 3
Dependent Claim
51 words
A synthetic, semi-crystalline inorganic oxide composition prepared by reacting a mixture of a non-ionic poly(alkylene oxide) derived surfactant as a template (N°) and a neutral inorganic oxide precursor (I°), followed by hydrolysis and crosslinking of the inorganic oxide precursor to provide the composition and having a disordered assembly of worm channels.
Claim 4
Dependent Claim
51 words
A synthetic, semi-crystalline inorganic oxide composition prepared by reacting a mixture of a non-ionic poly(alkylene oxide) derived surfactant as a template (N°) and a neutral inorganic oxide precursor (I°), followed by hydrolysis and crosslinking of the inorganic oxide precursor to provide the composition and having a disordered assembly of worm channels.
Claim 5
Dependent Claim
13 words
The composition of claim 2 wherein the template is removed from the composition.
Claim 6
Dependent Claim
13 words
The composition of claim 2 wherein the surfactant has a terminal hydroxyl group.
Claim 7
Dependent Claim
92 words
The composition of claim 2 which has the formula: nR-EO/A.sub.x O.sub.y wherein A X O Y is an anhydrous form of the composition, 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 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 0, x is about 1 and y is between about 1 and 3.
Claim 8
Dependent Claim
176 words
The composition of claim 2 which has the formula: nR-EO/A.sub.v G.sub.w Si.sub.x D.sub.y O.sub.z wherein A v G w Si x D y O z is an anhydrous form of the composition, 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 wherein when R-EO is present n is between about 0.01 and 1; A is at least one optional trivalent element selected from the group consisting of B, Cr, Al, Ga and Fe; G is at least one optional tetravalent metallic element selected from the group consisting of Sn, Ge, Ti, V, Hf and Zr; Si is silicon; D is optional and is a pentavalent or hexavalent element selected from the group consisting of Sb, Cr, Nb, Ta, V, W and Mo; O is oxygen and v, w, x, y and z are the molar stoichiometries of A, G, Si, D and O respectively, wherein in the composition when calcined, n is about 0, 0≦v≦2, 0≦w≦1, 0≦x≦1, 0.001≦y≦2and 1≦z≦3.
Claim 9
Dependent Claim
26 words
The composition of claim 2 having X-ray diffraction patterns with at least one reflection corresponding to a lattice spacing of between about 3 to 10 nm.
Claim 10
Dependent Claim
37 words
The composition of any one of claims 1 or 2 which after calcination, has an N 2 , O 2 or Ar adsorption-desorption isotherm that has a step at P/P O equal to between 0.2 and 0.7.
Claim 11
Dependent Claim
34 words
The composition of claim 8 wherein a ratio of textural to framework-confined mesoporosity as determined by the N 2 , O 2 or Ar adsorption isotherm is less than or equal to about 0.2.
Claim 12
Dependent Claim
21 words
The composition of claim 2 wherein said composition has a specific surface area between 300 and 1400 m 2 per gram.
Claim 13
Dependent Claim
25 words
The composition of claim 2 wherein a molar ratio of nonionic surfactant to inorganic oxide precursor in the reaction mixture is between 0.01 and 1.0.
Claim 14
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 15
Dependent Claim
26 words
The compositions of claim 1 having an N 2 adsorption-desorption isotherms and Horvath-Kawazoe pore size distribution selected from the group consisting of FIGS. 4A and 6A.
Claim 16
Dependent Claim
14 words
The composition of claim 2 in which the template has been removed by calcination.
Claim 17
Dependent Claim
15 words
The composition of claim 2 in which the template has been removed through solvent extraction.
Claim 18
Dependent Claim
15 words
The composition of claim 1 having an X-ray diffraction pattern as shown in FIG. 7.
Claim 19
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. 8A.
Claim 20
Dependent Claim
14 words
The composition of claim 6 in which the template has been removed by calcination.
Claim 21
Dependent Claim
15 words
The composition of claim 6 in which the template has been removed through solvent extraction.
Claim 22
Dependent Claim
54 words
The composition of any one of claims 1 or 2 in which at least one transition metal is dispersed or impregnated in the channels in the composition, selected from the group consisting of Rh, Nb, Re, Ag, Au, Cu, Co, Cr, Ni, Fe, Ir, Mo, Pt, Pd, Sn, Ti, V, W, Zn and Zr.
Claim 23
Dependent Claim
19 words
The composition of any one of claims 1 or 2 containing transition metal substituted organic macrocycles in the channels.
Claim 24
Dependent Claim
21 words
The composition of any one of claims 1 and 2 wherein the composition has surfaces functionalized by an alkyl metal alkoxide.
Claim 25
Dependent Claim
35 words
The composition of any one of claims 2 and 6 wherein upon removal of the template the composition has surfaces that have been functionalized by reaction with metal carboxylate precursors, silylation reagents or alkylating reagents.
Claim 26
Dependent Claim
48 words
The composition of any one of claims 1 or 2 wherein surfaces of the compositions have been functionalized by reaction of the composition upon removal of the template and calcination with various reagents selected from the group consisting of metal nitrates, chlorides, fluorides, silylation reagents and alkylation reagents.
Claim 27
Dependent Claim
23 words
The compositions of claim 2 wherein the template (N°) is selected from the group consisting of primary, secondary and tertiary fatty alcohol poly(ethoxylates).
Claim 28
Dependent Claim
15 words
The compositions of claim 2 wherein the nonionic template (N°) is an alkyl phenol poly-(ethoxylates).
Claim 29
Dependent Claim
15 words
The compositions of claim 2 wherein the nonionic template (N°) is a fatty acid ethoxylate.
Claim 30
Dependent Claim
17 words
The compositions of claim 2 wherein the nonionic template (N°) is a poly(ethylene oxide-propylene oxide) block co-polymer.
Claim 31
Dependent Claim
22 words
The composition of claim 2 wherein the template (N°) is selected from the group consisting of primary and secondary fatty amine poly(ethoxylate).
Claim 32
Dependent Claim
18 words
The composition of claim 2 wherein the template (N°) is a fatty acid poly(ethylene oxide-propylene oxide) block co-polymer.
Claim 33
Dependent Claim
21 words
The composition of claim 2 wherein the template (N°) is selected from the group consisting of fatty acid alkanolamides and ethoxylates.
Claim 34
Dependent Claim
21 words
The composition of claim 1 wherein the template (N°) is selected from the group consisting of sorbitan esters and sorbitan ethoxylates.
Claim 35
Dependent Claim
11 words
The composition of claim 1 wherein the inorganic oxide is alumina.
Claim 36
Dependent Claim
14 words
The composition of claim 1 wherein the template (N°) is a polyamine propoxylate ethoxylate.
Claim 37
Independent Claim
101 words
A method for the preparation of a synthetic semi-crystalline inorganic oxide composition which comprises: (a) mixing (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 to form a gel containing the composition; (b) separating at least some of the hydrolyzing agent and the surfactant from the gel to form the composition; and (c) optionally calcining the composition wherein the composition has a disordered assembly of worm channels.
Claim 38
Independent Claim
101 words
A method for the preparation of a synthetic semi-crystalline inorganic oxide composition which comprises: (a) mixing (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 to form a gel containing the composition; (b) separating at least some of the hydrolyzing agent and the surfactant from the gel to form the composition; and (c) optionally calcining the composition wherein the composition has a disordered assembly of worm channels.
Claim 39
Dependent Claim
24 words
The method of claim 35 wherein the gel is prepared by a random order of addition of the template and neutral inorganic oxide precursor.
Claim 40
Independent Claim
163 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, wherein the composition has a disordered assembly of worm channels.
Claim 41
Independent Claim
163 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, wherein the composition has a disordered assembly of worm channels.
Claim 42
Dependent Claim
34 words
The method of claim 37 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 43
Dependent Claim
15 words
The method of claim 37 wherein said inorganic oxide precursor solution is mixed without aging.
Claim 44
Dependent Claim
22 words
The method of claim 37 wherein the template is separated from the composition and as an additional step recycled after step (d).
Claim 45
Dependent Claim
29 words
The method of claim 40 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 46
Dependent Claim
26 words
The method of claim 37 wherein in step (a) the stirring is at a temperature of at least minus 20° C. for at least 5 minutes.
Claim 47
Dependent Claim
22 words
The method of claim 37 wherein the composition is calcined at about 300° to 1000° C. for at least about 30 minutes.
Claim 48
Dependent Claim
11 words
The method of claim 37 wherein the inorganic oxide is alumina.
Claim 49
Independent Claim
234 words
A method for the preparation of a semi-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 solution; (d) aging of the first precipitate with stirring; (e) redispersing 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 solution, lower alkanol and at least some of the template from the second precipitate by washing once with ethanol; (h) drying the second precipitate in air at ambient temperature to form the composition; (i) optionally heat treating the composition to at least 373° K in air for at least 16 hours; (j) optionally removing the template form the composition by solvent extraction; and (k) optionally calcining the composition at a temperature between about 673° K and 973° K in air for at least 4 hours to remove any remaining template and to cross-link the composition, wherein the composition has a disordered assembly of worm channels.
Claim 50
Independent Claim
234 words
A method for the preparation of a semi-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 solution; (d) aging of the first precipitate with stirring; (e) redispersing 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 solution, lower alkanol and at least some of the template from the second precipitate by washing once with ethanol; (h) drying the second precipitate in air at ambient temperature to form the composition; (i) optionally heat treating the composition to at least 373° K in air for at least 16 hours; (j) optionally removing the template form the composition by solvent extraction; and (k) optionally calcining the composition at a temperature between about 673° K and 973° K in air for at least 4 hours to remove any remaining template and to cross-link the composition, wherein the composition has a disordered assembly of worm channels.
Claim 51
Dependent Claim
13 words
The method of claim 45 wherein the calcining is by combustion in air.
Claim 52
Independent Claim
169 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 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 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 at a temperature between 673° K and 973° K in air for at least 4 hours to remove any remaining template and cross-link the composition, wherein the composition has a disordered assembly of worm channels.
Claim 53
Independent Claim
169 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 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 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 at a temperature between 673° K and 973° K in air for at least 4 hours to remove any remaining template and cross-link the composition, wherein the composition has a disordered assembly of worm channels.
Claim 54
Dependent Claim
13 words
The method of claim 47 wherein the calcining is by combustion in air.
Claim 55
Dependent Claim
91 words
In a method for cracking a petroleum product using a catalyst, the improvement which comprises using a catalyst which is a synthetic, semi-crystalline inorganic 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 1400 square meters per gram and having a disordered assembly of worm channels.
Claim 56
Dependent Claim
91 words
In a method for cracking a petroleum product using a catalyst, the improvement which comprises using a catalyst which is a synthetic, semi-crystalline inorganic 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 1400 square meters per gram and having a disordered assembly of worm channels.
Claim 57
Dependent Claim
11 words
The method of claim 49 wherein the inorganic oxide is alumina.
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