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US5800799A
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Porous inorganic oxide materials prepared by non-ionic surfactant and fluoride ion
Assignee: MERRY LAURIE A
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Filing: 1996-05-02
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Granted: 1998-09-01
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Expires: 2016-05-02
Abstract
Abstract A method for the preparation of new quasi-crystalline, porous inorganic oxide compositions formed in the presence of fluoride ion possessing a disordered assembly of worm-like channels. The method uses an interaction between various nonionic polyethylene oxide based surfactants (N DEG ) and neutral inorganic oxide precursors (I DEG ) in an aqueous solution and then the formation of dispersed particles in the aqueous solution in the presence of fluoride. This (N DEG I DEG F-) 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
- 👤 Eric P. Prouzet
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 21:22
CPC Classifications
C; C01; C01B; C01B37/00; C01B37/02
Claims Analysis
Total Claims: 54
Claim 1
Independent Claim
63 words
A synthetic, semi-crystalline mesoporous inorganic metal oxide composition containing fluoride ion having at least one resolved x-ray reflection corresponding to a lattice spacing of 3 to 10 nm, framework confined channels between 2 and 10 nm, and a specific surface area of 300 to 1400 square meters per gram and having a disordered array of channels of regular diameter in the mesoporous range.
Claim 2
Dependent Claim
63 words
A synthetic, semi-crystalline mesoporous inorganic metal oxide composition containing fluoride ion having at least one resolved x-ray reflection corresponding to a lattice spacing of 3 to 10 nm, framework confined channels between 2 and 10 nm, and a specific surface area of 300 to 1400 square meters per gram and having a disordered array of channels of regular diameter in the mesoporous range.
Claim 3
Dependent Claim
56 words
A synthetic, semi-crystalline inorganic metal oxide composition prepared by reacting a mixture of a non-ionic poly(alkylene oxide) derived surfactant as a template (N°) and a neutral metal inorganic oxide precursor (I°) in an aqueous hydrolyzing solution followed by addition of fluoride ion to provide the composition as a particulate dispersion which is separated from the solution.
Claim 4
Dependent Claim
56 words
A synthetic, semi-crystalline inorganic metal oxide composition prepared by reacting a mixture of a non-ionic poly(alkylene oxide) derived surfactant as a template (N°) and a neutral metal inorganic oxide precursor (I°) in an aqueous hydrolyzing solution followed by addition of fluoride ion to provide the composition as a particulate dispersion which is separated from the solution.
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
103 words
The composition of claim 2 which has the formula: nR--EO/A.sub.x O.sub.y wherein A x O y is written in anyhydrous form 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 and wherein when R--EO is present n is between about 0.01 and 1; 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
169 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 written in anhydrous form 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 and 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 Al, Ga and Fe; G 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, 0≦v≦2, 0≦w≦1, 0.001≦x≦1, 0≦y≦2 and 2≦z≦6.
Claim 9
Dependent Claim
25 words
The composition of claim 2 having X-ray diffraction patterns with at least one reflection corresponding to a lattice of between about 3 to 10 nm.
Claim 10
Dependent Claim
41 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 with a step centered at P/P 0 between 0.2 and 1.0 and at least one hysteresis loop.
Claim 11
Dependent Claim
35 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 about less than or equal to about 0.2.
Claim 12
Dependent Claim
21 words
The composition of claim 9 wherein the 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.
Claim 14
Dependent Claim
21 words
The composition of claim 1 having an X-ray diffraction pattern selected from the group consisting of FIGS. 3, 4 and 5.
Claim 15
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. 6 and 6A.
Claim 16
Dependent Claim
8 words
The composition of claim 2 containing the template.
Claim 17
Dependent Claim
14 words
The composition of claim 2 in which the template has been removed by calcination.
Claim 18
Dependent Claim
15 words
The composition of claim 2 in which the template has been removed through solvent extraction.
Claim 19
Dependent Claim
18 words
The composition of claim 1 having an X-ray diffraction pattern as shown in FIG. 3 as Pathway II.
Claim 20
Dependent Claim
22 words
The composition of claim 1 having N 2 adsorption-desorption isotherms and Horvath-Kawazoe pore size distribution as shown in FIGS. 7 and 7A.
Claim 21
Dependent Claim
8 words
The composition of claim 6 containing the template.
Claim 22
Dependent Claim
14 words
The composition of claim 6 in which the template has been removed by calcination.
Claim 23
Dependent Claim
15 words
The composition of claim 6 in which the template has been removed through solvent extraction.
Claim 24
Dependent Claim
51 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, 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 25
Dependent Claim
19 words
The composition of any one of claims 1 or 2 containing transition metal substituted organic macrocycles in the pores.
Claim 26
Dependent Claim
24 words
The composition of any one of claims 1 or 2 wherein the surfaces of the composition have been functionalized by an alkyl metal alkoxide.
Claim 27
Dependent Claim
39 words
The composition of any one of claims 2, 3, 4, 5 or 6 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
47 words
The composition of any one of claims 1 or 2 wherein surfaces of the composition have been functionalized by reaction of the composition upon removal of the template and calcination with one or more reagents selected from the group consisting of chlorides, fluorides, sylisation and alkylation reagents.
Claim 29
Dependent Claim
23 words
The composition of claim 2 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 2 wherein the nonionic template (N°) is an alkyl phenol poly-(ethoxylates).
Claim 31
Dependent Claim
15 words
The composition of claim 2 wherein the nonionic template (N°) is a fatty acid ethoxylate.
Claim 32
Dependent Claim
17 words
The composition of claim 2 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 2 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 2 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 2 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 2 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 2 wherein the template (N°) is a polyamine propoxylate ethoxylate.
Claim 38
Independent Claim
136 words
A method for the preparation of a synthetic semi-crystalline inorganic metal oxide composition which comprises: (a) 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) adding a fluoride ion to the mixture in an amount which produces a particulate dispersion of the inorganic oxide precursor and the significant; (c) separating at least some of the hydrolyzing agent and the surfactant from the particulate dispersion of step (b) to thereby form the inorganic metal oxide composition wherein the composition has a disordered array of channels of regular diameter in the mesoporous range; and (d) optionally calcining the composition.
Claim 39
Independent Claim
136 words
A method for the preparation of a synthetic semi-crystalline inorganic metal oxide composition which comprises: (a) 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) adding a fluoride ion to the mixture in an amount which produces a particulate dispersion of the inorganic oxide precursor and the significant; (c) separating at least some of the hydrolyzing agent and the surfactant from the particulate dispersion of step (b) to thereby form the inorganic metal oxide composition wherein the composition has a disordered array of channels of regular diameter in the mesoporous range; and (d) optionally calcining the composition.
Claim 40
Dependent Claim
28 words
The method of claim 36 wherein the mixture in step (a) is prepared by a random order of addition of the neutral template and neutral inorganic oxide precursor.
Claim 41
Independent Claim
188 words
A method for the preparation of a synthetic, semi-crystalline inorganic metal 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.; (d) adding a fluoride ion to the mixture in an amount which produces a particulate dispersion of the inorganic oxide and the surfactant; (e) separating at least some of the hydrolyzing agent and surfactant from the particulate dispersion of step (d), to thereby form the inorganic metal oxide composition; and (f) optionally calcining the composition, wherein the composition has a disordered array of channels of regular diameter in the mesoporous range.
Claim 42
Independent Claim
188 words
A method for the preparation of a synthetic, semi-crystalline inorganic metal 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.; (d) adding a fluoride ion to the mixture in an amount which produces a particulate dispersion of the inorganic oxide and the surfactant; (e) separating at least some of the hydrolyzing agent and surfactant from the particulate dispersion of step (d), to thereby form the inorganic metal oxide composition; and (f) optionally calcining the composition, wherein the composition has a disordered array of channels of regular diameter in the mesoporous range.
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 (e).
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
26 words
The method of claim 38 wherein in step (a) the solution aged at a temperature of between 20° to 100° C. for at least 120 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
142 words
A method for the preparation of a crystalline inorganic metal 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) mixing an inorganic metal precursor to the solution of step (a) at ambient temperature to form a homogeneous solution; (c) aging the homogeneous solution for between about 10 to 12 hours; (d) adding a fluoride to the mixture in an amount which produces a dispersion of the inorganic oxide and the surfactant; (e) aging the dispersions with the fluoride salt; (g) separating the aqueous solution, lower alkanol and at least some of the template from the dispersion; and (h) drying the dispersion to form the composition, wherein the composition has a disordered array of channels of regular diameter in the mesoporous range.
Claim 50
Independent Claim
142 words
A method for the preparation of a crystalline inorganic metal 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) mixing an inorganic metal precursor to the solution of step (a) at ambient temperature to form a homogeneous solution; (c) aging the homogeneous solution for between about 10 to 12 hours; (d) adding a fluoride to the mixture in an amount which produces a dispersion of the inorganic oxide and the surfactant; (e) aging the dispersions with the fluoride salt; (g) separating the aqueous solution, lower alkanol and at least some of the template from the dispersion; and (h) drying the dispersion to form the composition, wherein the composition has a disordered array of channels of regular diameter in the mesoporous range.
Claim 51
Dependent Claim
12 words
The method of claim 45 wherein the composition is calcined in air.
Claim 52
Independent Claim
138 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 mixture which is solid, precipitate; (c) adding a fluoride ion to the mixture in an amount which produces a particulate dispersion of the silicon dioxide and the surfactant; (d) separating the aqueous solution and template from the dispersion; (e) drying the separated dispersion in air at ambient temperature; (f) calcining the precipitate to remove the template between 673° K and 973° K in air to form the composition, wherein the composition has a disordered array of channels of regular diameter in the mesoporous range.
Claim 53
Independent Claim
138 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 mixture which is solid, precipitate; (c) adding a fluoride ion to the mixture in an amount which produces a particulate dispersion of the silicon dioxide and the surfactant; (d) separating the aqueous solution and template from the dispersion; (e) drying the separated dispersion in air at ambient temperature; (f) calcining the precipitate to remove the template between 673° K and 973° K in air to form the composition, wherein the composition has a disordered array of channels of regular diameter in the mesoporous range.
Claim 54
Dependent Claim
13 words
The method of claim 47 wherein the calcining is by combustion in air.
References Cited (Backward Citations)
DE286522C
Cited
US3702886A
Cited
US3709979A
Cited
US4151189A
Cited
US4108881A
Cited
US4391785A
Cited
US5098684A
Cited
US5102643A
Cited
US5300277A
Cited
US5334368A
Cited
US5350722A
Cited
US5143879A
Cited
US5320822A
Cited
US5308602A
Cited
US5622684A
Cited
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