The present invention relates to new organic-inorganic hybrid silicates and metal-silicates called ECS, characterized by an X-ray powder diffraction pattern with reflections exclusively at angular values higher than 4.0° of 2θ, preferably at angular values higher than 4.7°, and an ordered structure
The present invention relates to new organic-inorganic hybrid silicates and metal-silicates called ECS, characterized by an X-ray powder diffraction pattern with reflections exclusively at angular values higher than 4.0° of 2θ, preferably at angular values higher than 4.7°, and an ordered structure containing structural units having formula (a) wherein R is an organic group: Formula (a) and possibly containing one or more elements T selected from groups III B, IV B, V B and transition metals, with a Si/(Si +T) molar ratio in said structure higher than 0.3 and lower than or equal to 1, wherein Si is the silicon contained in the structural unit (a). A process is also described, starting from disilanes, for the preparation of these materials, which does not include the use of templates or surfactants. These materials can be used as molecular sieves, adsorbents, in the field of catalysis, in the field of electronics, in the field of sensors, in the field of nanotechnologies.
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1. An organic-inorganic hybrid silicate or metal-silicate, having an X-ray powder diffraction pattern with reflections exclusively at angular values higher than 4.0° of 2θ, and an ordered structure containing structural units having formula (a) wherein R is an organic group: and possibly containing
1. An organic-inorganic hybrid silicate or metal-silicate, having an X-ray powder diffraction pattern with reflections exclusively at angular values higher than 4.0° of 2θ, and an ordered structure containing structural units having formula (a) wherein R is an organic group: and possibly containing one or more elements T selected from the group consisting of a group III B element, a group IV B element, a group V B element, and a transition metal, with a Si/(Si+T) molar ratio in said structure higher than 0.3 and lower than or equal to 1, wherein Si is the silicon contained in the structural unit of formula (a). 2. The hybrid silicate or metal-silicate according to claim 1, having an X ray diffractogram with reflections exclusively at angular values higher than 4.7° of 2θ. 3. The hybrid silicate or metal-silicate according to claim 1, wherein the (a) units are connected with each other and with the element T, when present, through the oxygen atoms. 4. The hybrid silicate or metal-silicate according to claim 1, having signals in the 29Si-MAS-NMR spectrum whose chemical shifts fall between −40 and −90 ppm. 5. The hybrid silicate or metal-silicate according to claim 4, having signals in the 29Si-MAS-NMR spectrum whose chemical shifts essentially fall between −40 and −90 ppm. 6. The hybrid silicate or metal-silicate according to claim 4, whose the chemical shifts fall between −50 and −90 ppm. 7. The hybrid silicate or metal-silicate according to claim 1, wherein the Si/(Si+T) ratio is higher than or equal to 0.5 and lower than or equal to 1. 8. The hybrid silicate or metal-silicate according to claim 1, wherein T is at least one element selected from the group consisting of Si, Al, Fe, Ti, B, P, Ge, and Ga. 9. The hybrid silicate or metal-silicate according to claim 8, wherein T is at least one member selected from the group consisting of silicon, aluminum, and iron. 10. The hybrid silicate or metal-silicate according to claim 1, containing metal cations. 11. The hybrid silicate or metal-silicate according to claim 10, wherein the metal cation is at least one member selected from the group consisting of an alkaline, alkaline-earth metal, and lanthanide. 12. The hybrid silicate or metal-silicate according to claim 3, represented by formula (b): SiO1.5.xTO2.y/nMe.zC (b) wherein Si is the silicon contained in the structural unit (a), T is at least one element selected from the group consisting of a group IIIB element, a group IVB element, a group VB element, and a transition metal,Me is at least one cation of having a valence nC is carbonx ranges from 0 to 2y ranges from 0 to 2n is the valence of the cation Mez ranges between 0.5 and 10. 13. The hybrid silicate or metal-silicate according to claim 12, wherein x ranges from 0 to 1 and y ranges from 0 to 1. 14. The hybrid silicate or metal-silicate according to claim 1, wherein the organic group R is a hydrocarbon group with a number of carbon atoms lower than or equal to 20. 15. The hybrid silicate or metal-silicate according to claim 14, wherein the hydrocarbon group is an aliphatic group, an aliphatic group substituted with at least one group containing at least one heteroatom, an aromatic group, or an aromatic group substituted with at least one group containing at least one heteroatom. 16. The hybrid silicate or metal-silicate according to claim 15, wherein the aliphatic group is a linear, saturated group; a branched, saturated group; a linear, unsaturated group; or a branched, unsaturated group. 17. The hybrid silicate or metal-silicate according to claim 14, wherein R is selected from the group consisting of: —CH2—, —CH2CH2—, linear —C3H6—, branched —C3H6—, linear —C4H8—, branched —C4H8—, —C6H4—, —CH2—(C6H4)—CH2, —C2H4—(C6H4)—C2H4, —(C6H4)—(C6H4)—, —CH2—(C6H4)—(C6H4)—CH2, —C2H4—(C6H4)—(C6H4)—C2H4—, —CH═CH—, —CH═CH—CH2—, and CH2—CH═CH—CH2—. 18. The hybrid silicate or metal-silicate according to claim 1, having a pore diameter distribution centered within the range of mesopores, pore walls having an ordered structure, and a X-ray powder diffraction pattern containing the main reflections shown in Table 1 and FIG. 1: TABLE 1Intensity Nr2θ (°)[(I/I0) · 100 ]111.6100220.690323.476426.98530.06631.35735.526837.83944.731046.94. 19. The hybrid silicate or metal-silicate according to claim 18, wherein the pore diameter distribution is within the range of 2-30 nm. 20. The hybrid silicate or metal-silicate according to claim 18, wherein Si/(Si+T) is equal to or higher than 0.5 and lower than or equal to 1. 21. The hybrid silicate or metal-silicate according to claim 20, wherein Si/(Si+T) is higher than or equal to 0.5 and lower than 1. 22. The hybrid silicate or metal-silicate according to claim 20, wherein Si/(Si+T) is higher than or equal to 0.9 and lower than or equal to 1. 23. The hybrid silicate or metal-silicate according to claim 22, wherein T is aluminium, silicon or iron and Si/(Si+T) is higher than or equal to 0.9 and lower than 1. 24. The hybrid silicate or metal-silicate according to claim 21, wherein T is Si, a mixture of Si and Al or a mixture of Si and Fe, and the molar ratio Si/Al and Si/Fe in the mixtures is higher than or equal to 1. 25. The hybrid silicate or metal-silicate according to claim 1 having a crystalline structure and a X-ray powder diffraction pattern containing the main reflections shown in Table 2 and FIG. 1: TABLE 2Intensity Nr2θ (°)[(I/I0) · 100 ]16.76027.2100312.524413.367519.282620.136721.525825.184926.2351026.9291129.0331232.0211333.3551434.0181535.911. 26. The hybrid silicate or metal-silicate according to claim 1, having a crystalline structure and a X-ray powder diffraction pattern containing the main reflections shown in Table 3 and FIG. 1: TABLE 3Intensity Nr2θ (°)[(I/I0) · 100 ]19.0100212.671313.92414.95518.018619.212721.36823.344923.871024.371125.561225.7131326.6181430.071534.051639.45. 27. The hybrid silicate or metal-silicate according to claim 1, having crystalline structure and a X-ray powder diffraction pattern, containing the main reflections shown in table 4 and FIG. 1: TABLE 4Intensity Nr2θ (°)[(I/I0) · 100 ]15.61029.3100313.314414.29516.314618.59718.814819.816920.5271022.551123.4101226.591327.3231427.791529.0201629.891730.5101831.4121932.162036.410. 28. The hybrid silicate or metal-silicate according to claim 1, having a crystalline structure and a X-ray powder diffraction pattern containing the main reflections shown in table 5 and FIG. 3: TABLE 5Intensity Nr2θ (°)[(I/I0) · 100 ]14.910027.41239.87412.317512.519613.23714.823817.335918.0311019.4321119.8201220.891321.581422.491522.961623.731724.671824.8101926.582027.6252128.052228.772329.472429.982530.2102631.5152732.132832.88. 29. The hybrid silicate or metal-silicate according to claim 1, having a crystalline structure and a X-ray powder diffraction pattern containing the main reflections shown in table 6 and FIG. 5: TABLE 6Intensity Nr2θ (°)[(I/I0) · 100 ]15.110026.219312.212414.37515.536617.111717.520819.322920.511021.321123.3201225.921326.451427.4241528.2141631.3171731.9121832.241934.832038.342139.622249.16. 30. The hybrid silicate or metal-silicate according to claim 1, having a crystalline structure and a X-ray powder diffraction pattern containing the main reflections shown in table 7 and FIG. 7: TABLE 7Intensity Nr2θ (°)[(I/I0) · 100 ]14.62027.010039.311411.57512.23613.43714.118814.814916.3231018.121118.3101220.731320.841422.031523.171624.671725.621826.021926.232026.862127.5112228.462329.252429.732530.162633.06. 31. The hybrid silicate or metal-silicate according to claim 25, wherein the Si/(Si+T) ratio is higher than or equal to 0.5 and lower than or equal to 0.9. 32. The hybrid silicate or metal-silicate according to claim 31 containing an element T which is silicon, aluminium or iron. 33. A process for the preparation of a hybrid silicate or a metal-silicate according to claim 1 comprising: 1) adding a disilane of formula (c): X3Si—R—SiX3 (c)wherein R is an organic group andX is a substituent which can be hydrolyzed to an aqueous mixture comprisingat least one hydroxide of at least one metal Me selected from the group consisting of an alkaline metal and an alkaline-earth metal andpossibly one or more sources of one or more elements T selected from the group consisting of a group IIIB element, a group IVB element, a group VB element, and a transition metal,2) maintaining the mixture obtained under hydrothermal conditions, under autogenous pressure, for a period of time sufficient for forming a solid material,3) recovering the solid and drying it. 34. The process according to claim 33, wherein in step (1) one or more salts of the metal Me are present. 35. The process according to claim 33, wherein R is a hydrocarbon group with a number of carbon atoms lower than or equal to 20. 36. The process according to claim 35, wherein the hydrocarbon group is an aliphatic group, an aliphatic group substituted with at least one group containing at least one heteroatom, an aromatic group, or an aromatic group substituted with at least one group containing at least one heteroatom. 37. The process according to claim 36, wherein the aliphatic group is a linear, saturated group; a branched, saturated group; a linear, unsaturated group; or a branched, unsaturated group. 38. The process according to claim 35, wherein R is selected from the group consisting of: —CH2—, —CH2CH2—, linear —C3H6—, branched —C3H6—, linear —C4H8—, branched —C4H8—, —C6H4—, —CH2—(C6H4—CH2, —C2H4—(C6H4)—C2H4, —(C6H4)—(C6H4)—, —CH2—(C6H4)—(C6H4)—CH2, —C2H4—(C6H4)—(C6H4)—C2H4—, —CH═CH—, —CH═CH—CH2—, and CH2—CH═CH—CH2—. 39. The process according to claim 33, wherein X is an alkoxide group having the formula —OCmH2m+1, wherein m is an integer selected from 1, 2, 3 or 4, ora halogen selected from the group consisting of chlorine, fluorine, bromine and iodine. 40. The process according to claim 39, wherein X is an alkoxide group. 41. The process according to claim 33, wherein the compound having formula (c) is selected from the group consisting of: (CH3O)3Si—C4H8—CH2—C4H8—Si (OCH3)3,(CH3CH2O)3Si—C4H8—CH2—C4H8—Si(OCH2CH3)3,(CH3O)3Si—C4H8—CH2CH2—C4H8—Si(OCH3)3,(CH3CH2O)3Si—C4H8—CH2CH2—C4H8—Si(OCH2CH3)3,(CH3O)3Si—C4H8—C6H4—C4H8—Si(OCH3)3,(CH3CH2O)3Si—C4H8—C6H4—C4H8—Si(OCH2CH3)3,(CH3O)3Si—C4H8—CH2—C4H8—C6H4—C4H8—CH2—C4H8—Si(OCH3)3,(CH3CH2O)3Si—C4H8—CH2—C4H8—C6H4—C4H8—CH2—C4H8Si(OCH2CH3)3,(CH3O)3Si—C4H8—C6H4—C4H8—C6H4—C4H8—Si(OCH3)3,(CH3CH2O)3Si—C4H8—C6H4—C4H8—C6H4—C4H8—Si(OCH2CH3)3,(CH3O)3Si—C4H8—CH2—C4H8—C6H4—C4H8—C6H4—C4H8—CH2—C4H8—Si(OCH3)3 and(CH3CH2O)3Si—C4H8—CH2—C4H8—C6H4—C4H8—C6H4—C4H8—CH2—C4H8—Si(OCH2CH3)3. 42. The process according to claim 33, wherein the mixture of step (1) is prepared by mixing the reagents in the following proportions, expressed as molar ratios: Si/(Si+T) is higher than 0.3 and lower than or equal to 1Me+/Si=0.05-5OH−/Si=0.05-2H2O/Si<100wherein Si is the silicon contained in the disilane of formula (c). 43. The process according to claim 42, wherein the Si/(Si+T) ratio varies from 0.5 to 1. 44. The process according to claim 43, wherein the Si/(Si+T) ratio is higher than or equal to 0.5 and lower than 1. 45. The process according to claim 42, wherein the mixture of step (1) is prepared by mixing the reagents in the following proportions, expressed as molar ratios: Si/(Si+T)=0.5-0.9Me+/Si=0.1-2OH−/Si=0.1-1H2O/S=3-50. 46. The process according to claim 45 wherein the disilane is 1,4 bis(triethoxysilyl)-benzene. 47. The process according to claim 45, wherein the disilane is 4,4′bis(triethoxysilyl)1,1′diphenyl. 48. The process according to claim 45 wherein the molar ratios are: Si/(Si+T)=0.5-0.7Me+/Si=0.1-1.5OH−/Si=0.1-0.25H2O/Si=3-50wherein, Me=Na and T=Al, Si or Fe and the mixture is kept, in step (2), under hydrothermal conditions, at autogenous pressure, for a period of 2 to 28 days. 49. The process according to claim 45 wherein the molar ratios are: Si/(Si+T)=0.7-0.9Me+/Si=0.25-1.5OH−/Si=0.25-1. 50. The process according to claim 49, wherein the Si/(Si+T) ratio is higher than 0.7 and lower than or equal to 0.9. 51. The process according to claim 49, wherein Me=Na or Na+Li, T=Al, Si or Fe and the mixture is maintained, in step (2), under hydrothermal conditions, at autogenous pressure, for a time ranging from 2 to 50 days. 52. The process according to claim 45 wherein the molar ratios are: Si/(Si+T)=0.5-0.9Me+/Si=0.1-2.0OH−/Si=0.1-1wherein, Me is a mixture of Na+K and T=Al, Si or Fe and the mixture is kept, in step (2), under hydrothermal conditions, at autogenous pressure, for a period ranging from 2 to 50 days. 53. The process according to claim 42 wherein the molar ratios are: Si/(Si+T)=0.9-1Me+/Si=0.1-2OH−/Si=0.1-1H2O/Si=3-50. 54. The process according to claim 53, wherein the Si/(Si+T) ratio is higher than 0.9 and lower than 1. 55. The process according to claim 53 wherein, T is Al, Si or Fe, and the mixture of step (1) is prepared by mixing the reagents in the following proportions, expressed as molar ratios: Si/(Si+T)=is higher than or equal to 0.9 and lower than 1Me+/Si=0.1-2OH−/Si=0.1-1H2O/Si=3-50. 56. The process according to claim 55, wherein the disilane is 1,4 bis(triethoxysilyl)benzene. 57. The process according to claim 42, wherein T is Si or a mixture Si+Al or Si+Fe, characterized by a molar ratio Si/Al or Si/Fe≧1, wherein the molar ratios are: Si/(Si+T)=higher than 0.5, lower than 1Me+/Si=0.1-2OH−/Si=0.1-1H2O/Si=3-50. 58. The process according to claim 57, wherein the disilane present is 1,4 bis(triethoxysilyl)benzene. 59. The process according to claim 42, wherein the molar ratios are: Si/(Si+T)=0.5-0.9Me+/Si=0.1-2OH−/Si=0.1-1H2O/Si=3-50 and, the disilane is 1,4bis(triethoxysilyl-ethyl)benzene. 60. The process according to claim 42, wherein the molar ratios are: Si/(Si+T)=0.5-0.9Me+/Si=0.1-2OH−/Si=0.1-1H2O/Si=3-50 and, the disilane is 1,3 bis(triethoxysilyl)propane. 61. The process according to claim 33 wherein in step (1), the corresponding soluble salts or alkoxides are used as sources of the element T. 62. The process according to claim 33 wherein in step (1), the hydroxide of the alkaline metal is at least one of sodium hydroxide, potassium hydroxide, and lithium hydroxide. 63. The process according to claim 33 wherein in step (2), the mixture is maintained in an autoclave, under hydrothermal conditions, at autogenous pressure, and possibly under stirring, at a temperature ranging from 70 to 180° C., for a period of 1 to 50 days. 64. The process according to claim 63, wherein step (2) is effected at a temperature ranging from 80 to 150° C., for a period of 2 to 30 days. 65. The process according to claim 33, wherein the drying is effected at a temperature ranging from 50 to 80° C., for a period of 2 to 24 hours. 66. The hybrid silicate or metal-silicate according to claim 1, in the form of a molecular sieve. 67. The hybrid silicate or metal-silicate according to claim 1, in the form of an absorbent. 68. The hybrid silicate or metal-silicate according to claim 1, wherein the Si/(Si+T) ratio is higher than or equal to 0.5 and lower than 1.
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