SUPERFICIALLY POROUS MATERIALS COMPRISING A COATED CORE HAVING NARROW PARTICLE SIZE DISTRIBUTION; PROCESS FOR THE PREPARATION THEREOF; AND USE THEREOF FOR CHROMATOGRAPHIC SEPARATIONS

• US 20190015815A1
• Filed: 03/06/2017
• Published: 01/17/2019
• Est. Priority Date: 03/06/2016
• Status: Abandoned Application

• Current Assignee: Waters Technologies Corporation (Waters Corporation)
• Original Assignee: Waters Technologies Corporation (Waters Corporation)
• Inventors: Lawrence, Nicole L., Walsh, Daniel P., Fairchild, Jacob Nathan, Wyndham, Kevin Daniel
• Application Number:
  US16/082,803
• Publication Number:
  US 20190015815A1
• Time in Patent Office: Days
• CPC Class Codes: B01D 15/206 Packing or coating
• CPC Class Codes: B01J 20/22 comprising organic material
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28007 with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like carbon nanostructures B01J20/205
• CPC Class Codes: B01J 20/28009 Magnetic properties
• CPC Class Codes: B01J 20/28016 Particle form
• CPC Class Codes: B01J 20/28019 Spherical, ellipsoidal or cylindrical
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28059 being less than 100 m2/g
• CPC Class Codes: B01J 20/28061 being in the range 100-500 m2/g
• CPC Class Codes: B01J 20/28064 being in the range 500-1000 m2/g
• CPC Class Codes: B01J 20/28066 being more than 1000 m2/g
• CPC Class Codes: B01J 20/28069 Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/28071 being less than 0.5 ml/g
• CPC Class Codes: B01J 20/28073 being in the range 0.5-1.0 ml/g
• CPC Class Codes: B01J 20/28076 being more than 1.0 ml/g
• CPC Class Codes: B01J 20/28078 Pore diameter
• CPC Class Codes: B01J 20/28083 being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: B01J 20/28085 being more than 50 nm, i.e. macropores
• CPC Class Codes: B01J 20/28092 : Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
• CPC Class Codes: B01J 20/28095 : Shape or type of pores, voids, channels, ducts
• CPC Class Codes: B01J 20/28097 : being coated, filled or plugged with specific compounds
• CPC Class Codes: B01J 20/283 : based on silica
• CPC Class Codes: B01J 20/285 : based on polymers
• CPC Class Codes: B01J 20/286 : Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/32 : Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
• CPC Class Codes: B01J 20/3204 : Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3234 : Inorganic material layers
• CPC Class Codes: B01J 20/3236 : containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 20/324 : containing free carbon, e.g. activated carbon
• CPC Class Codes: B01J 20/3242 : Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
• CPC Class Codes: B01J 20/3257 : the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
• CPC Class Codes: B01J 20/3272 : Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3285 : Coating or impregnation layers comprising different type of functional groups or interactions, e.g. different ligands in various parts of the sorbent, mixed mode, dual zone, bimodal, multimodal, ionic or hydrophobic, cationic or anionic, hydrophilic or hydrophobic
• CPC Class Codes: B01J 20/3289 : Coatings involving more than one layer of same or different nature
• CPC Class Codes: B01J 20/3293 : Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
• CPC Class Codes: B01J 20/3295 : Coatings made of particles, nanoparticles, fibers, nanofibers
• CPC Class Codes: B01J 2220/46 : Materials comprising a mixture of inorganic and organic materials materials coated or impregnated on a carrier B01J20/32
• CPC Class Codes: B01J 2220/56 : Use in the form of a bed
• CPC Class Codes: B01J 2220/82 : Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds

Abstract

The present invention provides novel chromatographic materials, e.g., for chromatographic separations, processes for its preparation and separations devices containing the chromatographic material; separations devices, chromatographic columns and kits comprising the same; and methods for the preparation thereof. The chromatographic materials of the invention are chromatographic materials comprising having a narrow particle size distribution.

Claims

1. A superficially porous material comprising a coated core and one or more layers of a porous shell material surrounding the coated core, wherein said coated core comprises a substantially nonporous core material coated with a core-coating material.

2. The superficially porous material of claim 1, wherein the material is comprised of superficially porous particles.

3. The superficially porous material of claim 1, wherein the material is a superficially porous monolith.

4. The superficially porous material of claim 2, wherein the material has a substantially narrow particle size distribution.

5. The superficially porous material of claim 2, wherein the substantially nonporous core material has a substantially narrow particle size distribution.

6. The superficially porous material of claim 2, wherein the 90/10 ratio of particle sizes is from 1.00-1.55.

7. The superficially porous material of claim 6, wherein the 90/10 ratio of particle sizes is from 1.00-1.10.

8. The superficially porous material of claim 7, wherein the 90/10 ratio of particle sizes is from 1.05-1.10.

9. The superficially porous material of claim 6, wherein the 90/10 ratio of particle sizes is from 1.10-1.55.

10. The superficially porous material of claim 9, wherein the 90/10 ratio of particle sizes is from 1.10-1.50.

11. The superficially porous material of claim 10, wherein the 90/10 ratio of particle sizes is from 1.30-1.45.

12. The superficially porous material of claim 1, wherein the material has chromatographically enhancing pore geometry.

13. The superficially porous material of claim 12, wherein the material has a small population of micropores.

14. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is silica.

15. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is silica coated with a core-coating material and subsequently coated with an inorganic/organic hybrid material.

16. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a magnetic core material.

17. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a magnetic core material with a core-coating material and subsequently coated with silica.

18. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a high thermal conductivity core material.

19. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a high thermal conductivity core material coated with a core-coating material and subsequently coated with silica.

20. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a composite material.

21. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a composite material with a core-coating material and subsequently coated with an inorganic/organic hybrid material.

22. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a composite material with a core-coating material and subsequently coated with silica.

23. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a magnetic core material coated with a core-coating material and subsequently coated with an inorganic/organic hybrid material.

24. The superficially porous material of any one of claims 1-13, wherein the substantially nonporous core material is a high thermal conductivity core material coated with a core-coating material and subsequently coated with an inorganic/organic hybrid material.

25. The superficially porous material of any one of claims 20-24, wherein composite material comprises a magnetic additive material or a high thermal additive or a combination thereof.

26. The superficially porous material of any one of claims 1-25 wherein the porous shell material is a silica.

27. The superficially porous material of any one of claims 1-25 wherein the porous shell material is a composite material.

28. The superficially porous material of any one of claims 1-25 wherein the porous shell material is an inorganic/organic hybrid material.

29. The superficially porous material of any one of claims 1-25 comprising more than one layer of porous shell material wherein each layer is independently selected from an inorganic/organic hybrid material, silica, a composite material or mixtures thereof.

30. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is a composite material and the porous shell material is silica.

31. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is a composite material and the porous shell material is inorganic/organic hybrid material.

32. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is a composite material and the porous shell material is a composite material.

33. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is silica and the porous shell material is a composite material.

34. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is silica and the porous shell material is an inorganic/organic hybrid material.

35. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is a magnetic core material and the porous shell material is silica.

36. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is a magnetic core material and the porous shell material is an inorganic/organic hybrid material.

37. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is a magnetic core material and the porous shell material is a composite material.

38. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is a high thermal conductivity core material and the porous shell material is silica.

39. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core material is a high thermal conductivity core material and the porous shell material is an inorganic/organic hybrid material.

40. The superficially porous material of any one of claims 1-29 wherein the substantially nonporous core is a high thermal conductivity core material and the porous shell material is a composite material.

41. The superficially porous material of any one of claims 1-40, wherein the inorganic/organic hybrid material has the formula:

(SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m] 

 

(I)

wherein,

R and R¹ are each independently C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl;

R² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₁-C₁₈ heteroaryl;

or absent;

wherein each R² is attached to two or more silicon atoms;

p and q are each independently 0.0 to 3.0,

t is 0.5, 1.0, or 1.5;

d is 0 to about 30;

m is an integer from 1-20;

wherein R, R¹ and R² are optionally substituted;

provided that;

(1) when R² is absent, m=1 and t=(4−

(p+q))/2, when 0<

p+q≤

3; and

(2) when R² is present, m=2-20 and t=(3−

(p+q)), when p+q≤

2.

42. The superficially porous material of any one of claims 1-40, wherein the inorganic/organic hybrid material has the formula:

(SiO₂)_d/[(R)_p(R)_qSiO_t] 

 

(II)

wherein,

R and R¹ are each independently C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl;

d is 0 to about 30;

p and q are each independently 0.0 to 3.0, provided that when p+q=1 then t=1.5;

when p+q=2 then t=1;

or when p+q=3 then t=0.5.

43. The superficially porous material of any one of claims 1-40, wherein the inorganic/organic hybrid material has the formula:

(SiO₂)_d/[R²((R¹)_rSiO_t)_m] 

 

(III)

wherein,

R¹ is C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl;

R² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₁-C₁₈ heteroaryl;

or absent;

wherein each R² is attached to two or more silicon atoms;

d is 0 to about 30;

r is 0, 1 or 2, provided that when r=0 then t=1.5;

when r=1 then t=1;

or when r=2, then t=0.5; and

m is an integer from 1-20.

44. The superficially porous material of any one of claims 1-40, wherein the inorganic/organic hybrid material has the formula:

(A)_x(B)_y(C)_z 

 

(IV)

wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;

B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;

C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond;

x and y are positive numbers, and z is a non negative number, wherein x+y+z=1. In certain embodiments, z=0, then 0.002≤

x/y≤

210, and when z≠

0, then 0.0003≤

y/z≤

500 and 0.002≤

x/(y+z)≤

210.

45. The superficially porous material of any one of claims 1-40, wherein the inorganic/organic hybrid material has the formula:

(A)_x(B)_y(B*)_y*(C)_z 

 

(V)

wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;

B is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond, B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization;

C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond;

x, y and y*are positive numbers and z is a non negative number, wherein x+y+z=1. In certain embodiments, when z=0, then 0.002≤

x/(y+y*)≤

210, and when z≠

0, then 0.0003≤

(y+y*)/z≤

500 and 0.002≤

x/(y+y*+z)≤

210.

46. The superficially porous material of any one of claims 1-45, wherein the superficially porous material is a composite material which comprises a magnetic additive material.

47. The superficially porous material of claim 46, wherein the magnetic material has a mass magnetization at room temperature greater than 15 emu/g.

48. The superficially porous material of claim 46, wherein the magnetic material is a ferromagnetic material.

49. The superficially porous material of claim 46, wherein the magnetic material is a ferrimagnetic material.

50. The superficially porous material of claim 46, wherein the magnetic additive material is a magnetite;

maghemite;

yttrium iron garnet;

cobalt;

CrO₂;

a ferrite containing iron and Al, Mg, Ni, Zn, Mn or Co;

or a combination thereof.

51. The superficially porous material of any one of claims 1-50, wherein the magnetic core material has a mass magnetization at room temperature greater than 15 emu/g.

52. The superficially porous material of claim 51, wherein the magnetic material is a ferromagnetic material.

53. The superficially porous material of claim 51, wherein the magnetic material is a ferrimagnetic material.

54. The superficially porous material of claim 51, wherein the magnetic additive material is a magnetite;

maghemite;

yttrium iron garnet;

cobalt;

CrO₂;

a ferrite containing iron and Al, Mg, Ni, Zn, Mn or Co;

or a combination thereof.

55. The superficially porous material of any one of claims 1-54, wherein the composite material comprises a high thermal conductivity additive.

56. The superficially porous material of claim 55, wherein the high thermal conductivity additive is crystalline or amorphous silicon carbide, aluminum, gold, silver, iron, copper, titanium, niobium, diamond, cerium, carbon, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, or an oxide or a nitride thereof, or combinations thereof.

57. The superficially porous material of claim 56, wherein the high thermal conductivity additive is diamond.

58. The superficially porous material of any one of claims 1-57, wherein the high thermal conductivity core material is crystalline or amorphous silicon carbide, aluminum, gold, silver, iron, copper, titanium, niobium, diamond, cerium, carbon, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, or an oxide or a nitride thereof, or combinations thereof.

59. The superficially porous material of claim 58, wherein the high thermal conductivity core material is diamond.

60. The superficially porous material of any one of claims 1-59, wherein the material has a highly spherical core morphology.

61. The superficially porous material of any one of claims 1-59 wherein the material has a rod shaped core morphology.

62. The superficially porous material of any one of claims 1-59 wherein the material has a bent-rod shaped core morphology.

63. The superficially porous material of any one of claims 1-59 wherein the material has a toroid shaped core morphology.

64. The superficially porous material of any one of claims 1-59 wherein the material has a dumbbell shaped core morphology.

65. The superficially porous material of any one of claims 1-59 wherein the material has a mixture of highly spherical, rod shaped, bent-rod shaped, toroid shaped or dumbbell shaped core morphologies.

66. The superficially porous material of any one of claims 1-59, wherein the substantially nonporous core material is silica;

the porous shell material is silica; and

the material has a rod shaped, bent-rod shaped, toroid shaped or dumbbell shaped core morphology or a mixture thereof.

67. The superficially porous material of any one of claims 1-66 having a significantly higher thermal conductivity than a fully porous silica particle of the same size.

68. The superficially porous material of any one of claims 1-66 having a significantly higher thermal conductivity than a superficially porous silica particles of the same size.

69. The superficially porous material of any one of claims 1-68 capable of forming packed beds with improved permeability as compared to a fully porous silica particles of the same size.

70. The superficially porous material of any one of claims 1-68 capable of forming packed beds with improved permeability as compared to a superficially porous silica particles of the same size.

71. The superficially porous material of any one of claims 1-70 having improved chemical stability to high pH mobile phases as compared to an unbonded, fully porous silica particles of the same size.

72. The superficially porous material of any one of claims 1-70 having improved chemical stability to high pH mobile phases as compared to an unbonded, superficially porous silica particles of the same size.

73. The superficially porous material of any one of claims 1-72, wherein the porous shell layer is independently from 0.05 μ

m to 5 μ

m in thickness as measured perpendicular to the surface of the coated core.

74. The superficially porous material of claim 73, wherein the porous shell layer is independently from 0.06 μ

m to 1 μ

m in thickness as measured perpendicular to the surface of the coated core.

75. The superficially porous material of claim 73, wherein the porous shell layer is independently from 0.20 μ

m to 0.70 μ

m. in thickness as measured perpendicular to the surface of the coated core.

76. The superficially porous material of any one of claims 1-75, wherein the coated core has a particle size of 0.5-10 μ

m.

77. The superficially porous material of claim 76, wherein the coated core has a particle size of 0.8-5.0 μ

m.

78. The superficially porous material of claim 77, wherein the coated core has a particle size of 1.3-3.0 μ

m.

79. The superficially porous material of any one of claims 1-78, wherein the average particle size of the material is between 0.8-20.0 μ

m.

80. The superficially porous material of claim 79, wherein the average particle size of the material is between 1.1-5.0 μ

m.

81. The superficially porous material of claim 80, wherein the average particle size of the material is between 1.3-2.9 m.

82. The superficially porous material of any one of claims 1-80, wherein the pores of the material have an average diameter of about 25-600 Å

.

83. The superficially porous material of claim 82, wherein the pores of the material have an average diameter of about 60-350 Å

.

84. The superficially porous material of claim 83, wherein the pores of the material have an average diameter of about 80-300 Å

.

85. The superficially porous material of claim 84, wherein the pores of the material have an average diameter of about 90-150 Å

.

86. The superficially porous material of any one of claims 1-85, wherein the average pore volume of the material is of about 0.09-0.80 cm³/g.

87. The superficially porous material of claim 86, wherein the average pore volume of the material is of about 0.11-0.45 cm³/g.

88. The superficially porous material of claim 87, wherein the average pore volume of the material is of about 0.17-0.30 cm³/g.

89. The superficially porous material of any one of claims 1-88, wherein pore surface area of the material is between about 10 m²/g and 600 m²/g.

90. The superficially porous material of claim 89, wherein pore surface area of the material is between about 15 m²/g and 300 m²/g.

91. The superficially porous material of claim 90, wherein pore surface area of the material is between about 60 m²/g and 200 m²/g.

92. The superficially porous material of any one of claims 1-91, which has been further surface modified.

93. The superficially porous material of any one of claims 1-92, which has been further surface modified by:

coating with a polymer;

by coating with a polymer by a combination of organic group and silanol group modification;

a combination of organic group modification and coating with a polymer;

a combination of silanol group modification and coating with a polymer;

formation of an organic covalent bond between the material'"'"'s organic group and a modifying reagent;

or

a combination of organic group modification, silanol group modification and coating with a polymer.

94. The superficially porous material of any one of claims 1-93, wherein said superficially porous material has a smooth surface.

95. The superficially porous material of claim 1-94, wherein the core-coating material is composed of a material which enhances one or more of the characteristics selected from the group consisting of chromatographic selectivity, particle chemical stability, column efficiency, and mechanical strength.

96. The superficially porous material of claim 95, wherein the core-coating material is composed of a material which provides advantages in chromatographic separation.

97. The superficially porous material of claim 95, wherein the core-coating material is composed of a material which provides a change in hydrophilic/lipophilic balance (HLB), surface charge (e.g., isoelectric point or silanol pKa), and/or surface functionality for enhanced chromatographic separation.

98. The superficially porous material of claim 1-97, wherein the core-coating material is an inorganic material;

an organic material;

or an inorganic/organic hybrid material.

99. The superficially porous material of claim 1-98, wherein the coated core is derived from

condensation of one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on the surface of the core, or

application of partially condensed polymeric organofunctional metal precursors, a mixture of two or more polymeric organofunctional metal precursors, or a mixture of one or more polymeric organofunctional metal precursors with a polymeric metal oxide precursors on the surface of the core.

100. The superficially porous material of claims 1-99, wherein the inorganic portion of the core-coating material is selected from the group consisting of alumina, silica, titania, cerium oxide, or zirconium oxides, and ceramic materials.

101. The superficially porous material of claims 1-100, wherein the inorganic portion of the core-coating material is silica.

102. The superficially porous material of claims 1-98, wherein the coated core is derived from

condensation of one or more organofunctional silanes and/or tetraalkoxysilane on the surface of the core, or

application of partially condensed organofunctional silane, a mixture of two or more organofunctional silanes, or a mixture of one or more organofunctional silanes with a tetraalkoxysilane on the surface of the core.

103. The superficially porous material of claims 1-102, wherein a hybrid content of the core-coating material ranges from about 0-100 mol % hybrid.

104. The superficially porous material of claims 1-98, wherein the core-coating material is independently selected from alumina, silica, titanium oxide, zirconium oxide and ceramic materials.

105. The superficially porous material of claims 1-98, wherein the core-coating material is silica.

106. The superficially porous material of claims 1-98, wherein a structure of the core-coating material comprises a copolymeric structure.

107. The superficially porous material of claims 1-98, wherein the core-coating material comprises an inorganic/organic hybrid material having an inorganic portion and an organic portion.

108. The superficially porous material of claim 107, wherein an inorganic portion of the core-coating material is present in an amount ranging from about 0 molar % to not more than about 25 molar %.

109. The superficially porous material of claim 107, wherein the inorganic portion of the core-coating material is present in an amount ranging from about 25 molar % to not more than about 50 molar %.

111. The superficially porous material of claim 109, comprising SiO₂ in an amount ranging from about 0 molar % to not more than about 25 molar %.

112. The superficially porous material of claim 109, comprising SiO₂ in an amount ranging from about 25 molar % to not more than about 50 molar %.

113. The superficially porous material of claims 1-98, wherein the core-coating material comprises a material of formula I:

(SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m];

 

 

(I)

wherein,

R and R¹ are each independently C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl;

R² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₁-C₁₈ heteroaryl;

or absent;

wherein each R² is attached to two or more silicon atoms;

p and q are each independently 0.0 to 3.0;

t is 0.5, 1.0, or 1.5;

d is 0 to about 30;

m is an integer from 1-20;

wherein R, R¹ and R² are optionally substituted;

provided that;

(1) when R² is absent, m=1 and t=(4−

(p+q))/2, when 0<

p+q≤

3; and

(2) when R² is present, m=2-20 and t=(3−

(p+q))/2, when p+q≤

2.

114. The superficially porous material of claim 113, wherein R² is absent.

115. The superficially porous material of claim 113, wherein R² is present.

116. The superficially porous material of claims 1-98, wherein the core-coating material comprises a material of formula II:

(SiO₂)_d/[(R)_p(R¹)_qSiO_t] 

 

(II);

wherein,

R and R¹ are each independently C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl;

d is 0 to about 30;

p and q are each independently 0.0 to 3.0, provided that when p+q=1 then t=1.5;

when p+q=2 then t=1;

or when p+q=3 then t=0.5.

117. The superficially porous material of claims 1-98, wherein the core-coating material comprises a material of formula III:

(SiO₂)_d/[R²((R¹)_rSiO_t)_m] 

 

(III)

wherein,

R¹ is C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl;

R² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₁-C₁₈ heteroaryl;

or absent;

wherein each R² is attached to two or more silicon atoms;

d is 0 to about 30;

r is 0, 1 or 2, provided that when r=0 then t=1.5;

or when r=1 then t=1;

or when r=2 then t=0.5; and

m is an integer from 1-20.

118. The superficially porous material of claims 1-98, wherein the core-coating material comprises a material of formula IV:

(A)x(B)y(C)z 

 

(IV),

wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;

B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;

C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and

x and y are positive numbers and z is a non negative number, wherein when z=0, then 0.002≤

x/y≤

210, and when z≠

0, then 0.0003≤

y/z≤

500 and 0.002≤

x/(y+z)≤

210.

119. The superficially porous material of claims 1-98, wherein the inorganic/organic surrounding material comprises a material of formula V:

(A)x(B)y(B*)y*(C)z 

 

(V),

wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;

B is an organosiloxane repeat units which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;

B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization;

C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond; and

x, y, and y* are positive numbers and z is a non negative number, wherein when z=0, then 0.002≤

x/(y+y*)≤

210, and when z≠

0, then 0.0003≤

(y+y*)/z≤

500 and 0.002≤

x/(y+y*+z)≤

210.

120. The superficially porous material of claims 1-98, wherein the nonporous core and/or the core-coating material is a hybrid inorganic/organic material comprising ordered domains having formula IV, V or VI below:

(A)_x(B)_y(C)_z 

 

(Formula IV)

wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;

B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;

C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and

x, y are positive numbers and z is a non negative number, wherein

when z=0, then 0.002≤

x/y≤

210, and when z≠

0, then

0.0003≤

y/z≤

500 and 0.002≤

x/(y+z)≤

210;

(A)_x(B)_y(B*)_y*(C)_z 

 

(Formula V)

wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;

B is an organosiloxane repeat units which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;

B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization;

C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond; and

x, y are positive numbers and z is a non negative number, wherein

when z=0, then 0.002≤

x/(y+y*)≤

210, and when z≠

0, then

0.0003≤

(y+y*)/z≤

500 and 0.002≤

x/(y+y*+z)≤

210;

or

[A]_y[B]_x 

 

(Formula VI),

wherein x, y, and y* are whole number integers and A is

SiO₂/(R¹_pR²_qSiO_t)_n or SiO₂/[R³(R¹_rSiO_t)_m]n;

wherein R¹ and R² are independently a substituted or unsubstituted C₁ to C₇ alkyl group, or a substituted or unsubstituted aryl group, R³ is a substituted or unsubstituted C₁ to C₇ alkyl, alkenyl, alkynyl, or arylene group bridging two or more silicon atoms, p and q are 0, 1, or 2, provided that p+q=1 or 2, and that when p+q=1, t=1.5, and when p+q=2, t=1;

r is 0 or 1, provided that when r=0, t=1.5, and when r=1, t=1;

m is an integer greater than or equal to 2; and

n is a number from 0.01 to 100;

B is;

SiO₂/(R⁴_vSiO_t)_n

wherein R⁴ is hydroxyl, fluorine, alkoxy, aryloxy, substituted siloxane, protein, peptide, carbohydrate, nucleic acid, or combinations thereof, R⁴ is not R¹, R², or R³;

v is 1 or 2, provided that when v=1, t=1.5, and when v=2, t=1; and

n is a number from 0.01 to 100;

wherein the material of formula VI has an interior area and an exterior surface, and said interior area of said material has a composition represented by A;

said exterior surface of said material has a composition represented by A and B, and wherein said exterior composition is between about 1 and about 99% of the composition of B and the remainder comprising A.

121. The superficially porous material of claim 119 wherein diffraction peak maxima observed for said material of formula IV, V or VI, exhibit a 20 position that excludes diffraction peaks resulting from atomic-range order that are associated with amorphous material.

122. The superficially porous material of claim 119, wherein said inorganic portion of said core-coating material of formula IV, V or VI is selected from the group consisting of alumina, silica, titania, cerium oxide, or zirconium oxides, and ceramic materials.

123. The superficially porous material of claim 122, wherein said inorganic portion of said core-coating material is silica.

124. The superficially porous material of claim 119, wherein the percentage by mass of ordered domains of said core-coating material ranges from about 1% to about 100%.

125. The superficially porous material of claims 1-124, wherein the coated core has a surface area of about 2 to 1100 m²/g.

126. The superficially porous material of claim 125, wherein the coated core has a surface area of about 2 to 100 m²/g.

127. The superficially porous material of claim 126, wherein the coated core has a surface area of about 2 to 50 m²/g.

128. The superficially porous material of claim 127, wherein the coated core has pore volume of less than about 10 cm²/g.

129. The superficially porous material of claims 1-128, wherein the coated core has an average size of about 0.1 μ

m to about 300 μ

m.

130. The superficially porous material of claim 129, wherein the coated core has an average size of about 0.1 μ

m to about 30 μ

m.

131. The superficially porous material of claims 1-130, wherein the coating of core-coating material on the coated core has an average thickness of about 0.001 nm to about 200 nm.

132. The superficially porous material of claim 131, wherein the coating of core-coating material on the coated core has an average thickness of about 0.01 nm to about 100 nm.

133. The superficially porous material of claim 132, wherein the coating of core-coating material on the coated core has an average thickness of about 0.1 nm to about 50 nm.

134. The superficially porous material of claims 1-133, wherein the coated core is hydrolytically stable at a pH of about 1 to about 14.

135. The superficially porous material of claim 134, wherein the coated core is hydrolytically stable at a pH of about 10 to about 14.

136. The superficially porous material of claim 134, wherein the coated core is hydrolytically stable at a pH of about 1 to about 5.

137. The superficially porous material of claims 1-136, wherein the organic content is from about 10 to about 40% carbon.

138. The superficially porous material of claim 137, wherein the organic content is from about 25 to about 40% carbon.

139. The superficially porous material of claim 138, wherein the organic content is from about 15 to about 35% carbon.

140. The superficially porous material of claim 139, wherein the organic content is from about 25 to about 35% carbon.

141. The superficially porous material of claim 41, 42, 43, 113, 116 or 117, wherein R¹ is C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, or C₁-C₁₈ alkyl.

142. The superficially porous material of claim 41, 42, 43, 113, 116 or 117, wherein R² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, or C₁-C₁₈ heteroaryl.

143. The superficially porous material of claim 41, 42, 43, 113, 116 or 117, wherein p is 0, q is 0, t is 1.5, m is 2, and R² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, or C₁-C₁₈ heteroaryl;

and wherein each R² is attached to two or more silicon atoms.

144. The superficially porous material of claim 143, wherein d is 0.

145. The superficially porous material of claim 143, wherein d is 0.11.

146. The superficially porous material of claim 143, wherein d is 0.33.

147. The superficially porous material of claim 143, wherein d is 0.83.

148. The superficially porous material of claim 41, 42, 43, 113, 116 or 117, wherein d is 0, q is 0, and R² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, or C₁-C₁₈ heteroaryl;

and wherein each R² is attached to two or more silicon atoms.

149. The superficially porous material of claim 148, wherein p is 0, 1, or 2.

150. The superficially porous material of claim 148, wherein t is 1.0 or 1.5.

151. The superficially porous material of claim 148, wherein m is 1 or 2.

152. The superficially porous material of claims 1-151, wherein said coated core has been surface modified with a surface modifier having the formula Z_a(R′

)_bSi—

R″

, where Z═

Cl, Br, I, C₁-C₅ alkoxy, dialkylamino or trifluoromethanesulfonate;

a and b are each an integer from 0 to 3 provided that a+b=3;

R′

is a C₁-C₆ straight, cyclic or branched alkyl group, and R″

is a functionalizing group.

153. The superficially porous material of claims 1-151, wherein said coated core has been surface modified by coating with a polymer.

154. The superficially porous material of claim 152, wherein R′

is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.

155. The superficially porous material of claim 152, wherein the functionalizing group R″

is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, an alkyl or aryl group containing an embedded polar functionality and a chiral moiety.

156. The superficially porous material of claim 152, wherein said functionalizing group R″

is a C₁-C₃₀ alkyl group.

157. The superficially porous material of claim 152, wherein said functionalizing group R″

comprises a chiral moiety.

158. The superficially porous material of claim 152, wherein said functionalizing group R″

is a C₁-C₂₀ alkyl group.

159. The superficially porous material of claim 152, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane and octadecyldimethylchlorosilane.

160. The superficially porous material of claim 159, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.

161. The superficially porous material of claims 1-160, wherein said coated core has been surface modified by a combination of organic group and silanol group modification.

162. The superficially porous material of claim 161, wherein said coated core has been surface modified by a combination of organic group modification and coating with a polymer.

163. The superficially porous material of claim 161, wherein said organic group comprises a chiral moiety.

164. The superficially porous material of claim 161, wherein said coated core has been surface modified by a combination of silanol group modification and coating with a polymer.

165. The superficially porous material of claim 161, wherein said coated core has been surface modified via formation of an organic covalent bond between the material'"'"'s organic group and the modifying reagent.

166. The superficially porous material of claim 161, wherein said coated core has been surface modified by a combination of organic group modification, silanol group modification and coating with a polymer.

167. The superficially porous material of claim 161, wherein said coated core has been surface modified by silanol group modification.

168. The superficially porous material of claims 1-167, wherein said coated core has been surface modified by organic group modification.

169. The superficially porous material of claim 168, wherein said coated core has been surface modified by a combination of organic group and silanol group modification.

170. The superficially porous material of claims 1-160, further comprising a nanoparticle dispersed within the material.

171. The superficially porous material of claim 170, wherein nanoparticle is a mixture of more than one nanoparticle.

172. The superficially porous material of claim 170, wherein the nanoparticle is present in <

20% by weight of the nanocomposite.

173. The superficially porous material of claim 170, wherein the nanoparticle is present in <

5% by weight of the nanocomposite.

174. The superficially porous material of claim 170, wherein the nanoparticle is crystalline or amorphous.

175. The superficially porous material of claim 170 or 171, wherein the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, oxides thereof, and nitrides thereof.

176. The superficially porous material of claim 175, wherein the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of nano-diamonds, silicon carbide, titanium dioxide, cubic-boronitride.

177. The superficially porous material of claim 170 or 171, wherein the nanoparticles are less than or equal to 200 μ

m in diameter.

178. The superficially porous material of claim 170 or 171, wherein the nanoparticles are less than or equal to 100 μ

m in diameter.

179. The superficially porous material of claim 170 or 171, wherein the nanoparticles are less than or equal to 50 μ

m in diameter.

180. The superficially porous material of claim 170 or 171, wherein the nanoparticles are less than or equal to 20 μ

m in diameter.

202. The method for preparing a superficially porous material of any one of claims 172-201, wherein each layer of porous shell material is applied using alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof, comprising the steps of:

a) condensing siloxane precursors on the substantially nonporous core in a reaction mixture comprising ethanol, water and ammonium hydroxide and optionally containing a non-ionic surfactant, an ionic surfactant, a polyelectrolyte or a polymer to form the porous shell material; and

b) introducing porosity through extraction, degradation, oxidation, hydrolysis, deprotection, or transformation of the hybrid group, ionic surfactant or non-ionic surfactant or a combination thereof.

248. A separations device having a stationary phase comprising the superficially porous material of any one of claims 1-181.

249. The separations device of claim 248, wherein said device is selected from the group consisting of chromatographic columns, thin layer plates, filtration membranes, microfluidic separation devices, sample cleanup devices, solid supports, solid phase extraction devices, microchip separation devices, and microtiter plates.

250. The separations device of claim 249, wherein the separations device is useful for applications selected from the group consisting of solid phase extraction, high pressure liquid chromatography, ultra high pressure liquid chromatography, combinatorial chemistry, synthesis, biological assays, ultra performance liquid chromatography, ultra fast liquid chromatography, ultra high pressure liquid chromatography, supercritical fluid chromatography, and mass spectrometry.

251. The separations device of claim 250, wherein the separations device is useful for biological assays and wherein the biological assays are affinity assays or ion-exchanged assays.

252. A chromatographic column, comprising

a) a column having a cylindrical interior for accepting a packing material and

b) a packed chromatographic bed comprising the superficially porous material of any one of claims 1-181.

253. A chromatographic device, comprising

a) an interior channel for accepting a packing material and

b) a packed chromatographic bed comprising the superficially porous material of any one of claims 1-181.

254. A kit comprising the superficially porous material of any one of claims 1-181, and instructions for use.

255. The kit of claim 254, wherein the instructions are for use with a separations device.

256. The kit of claim 255, wherein the separations device is selected from the group consisting of chromatographic columns, thin layer plates, microfluidic separation devices, solid phase extraction devices, filtration membranes, sample cleanup devices and microtiter plates.

110. The superficially porous material of claim 1067 wherein an inorganic portion of the core-coating material is independently selected from the group consisting of alumina, silica, titanium oxide, cerium oxide, zirconium oxide and ceramic materials.

181. An inorganic/organic hybrid particle comprising an inorganic/organic hybrid particle core and a core-coating material wherein said particle has the formula (Y(CH2)nSiO1.5)x(O 1.5SiCH2CH2SiO 1.5)y(SiO2)z wherein:

each Y is independently —

OH, —

NH2, —

NR2, —

NR2R′

+, SH, S(O)O-2R, S(O)0-2O—

, C1-C18 alkoxy, C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl, C1-C18 heterocycloalkyl, C5-C18 aryl, C5-C18 aryloxy, or C1-C18 heteroarylaryl, C1-C18 alkoxy, C1-C18 alkyl, C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl, C1-C18 heterocycloalkyl, C5-C18 aryl, C5-C18 aryloxy, or C1-C18 heteroaryl;

each R and R′

are independently C1-C18 alkoxy, C1-C18 alkyl, C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl, C1-C18 heterocycloalkyl, C5-C18 aryl, C5-C18 aryloxy, or C1-C18 heteroaryl;

n is from 0 to 18; and

x, y and z are independently from about 0.0 to about 1.0 wherein y+z is 1.0−

x and y is from about 3.0 to about 5.0 times greater than z.

182. A method for preparing a superficially porous material comprising:

a.) providing a substantially nonporous core material;

b.) coating said core material with a core-coating material to form a coated core material; and

c.) applying to said coated core material one or more layers of porous shell material

to form a superficially porous material

183. The method for preparing a superficially porous material of claim 182, further comprising the step of:

d.) optimizing one or more properties of the superficially porous material.

184. The method for preparing a superficially porous material of any one of claims 182-183, wherein substantially nonporous core material is silica, silica coated with an inorganic/organic hybrid surrounding material, magnetic core material, a magnetic core material coated with silica, a high thermal conductivity core material, a high thermal conductivity core material coated with silica, a composite material, a composite material coated with an inorganic/organic hybrid surrounding material, a composite material coated with silica, a magnetic core material coated with an inorganic/organic hybrid surrounding material, a high thermal conductivity core material coated with an inorganic/organic hybrid surrounding material, an inorganic core material, or an inorganic core material coated with another inorganic material.

185. The method for preparing a superficially porous material of claim 184, wherein substantially nonporous core material is a composite material and said composite material comprises a magnetic additive material, a high thermal conductivity additive material or a mixture thereof.

186. The method for preparing a superficially porous material of claim 184, wherein substantially nonporous core material comprises a coated or not coated particle.

187. The method for preparing a superficially porous material of claim 186, where the particle is diamond.

188. The method for preparing a superficially porous material of claim 186, where the particle is magnetite.

189. The method for preparing a superficially porous material of claim 184, wherein the substantially nonporous core material is silica having a highly spherical particle morphology and wherein each layer of porous shell material is independently selected from a porous inorganic/organic hybrid material, a porous composite material or mixtures thereof.

190. The method for preparing a superficially porous material of any one of claims 182-189, wherein each layer of porous shell material is independently selected from a porous inorganic/organic hybrid material, a porous silica, a porous composite material or mixtures thereof.

191. The method for preparing a superficially porous material of any one of claims 182-190, wherein each layer of porous shell material is applied using sols, a polyelectrolyte or a chemically degradable polymer, wherein:

a) the sols are inorganic sols, hybrid sols, nanoparticles, or mixtures thereof.

b) the polyelectrolyte or chemically degradable polymer is removed from the material using chemical extraction, degradation, or thermal treatment at temperatures less than 600°

C., or combinations thereof.

192. The method for preparing a superficially porous material of any one of claims 182-191, wherein each layer of porous shell material is applied by formation through an electrostatic or acid/base interaction of an ionizable group comprising the steps of:

a) prebonding the substantially nonporous core with an alkoxysilane that has an ionizable group,

b) treating the substantially nonporous core to sols that are inorganic, hybrid, nanoparticle, or mixtures thereof, that have been prebonded with an alkoxysilane that has an ionizable group of the opposite charge to the ionizable group on the surface of the core; and

c) forming additional layers on the material with sols that are inorganic, hybrid, nanoparticle, or mixtures thereof that have been prebonded with an alkoxysilane that has an ionizable group of opposite charge to the ionizable group of prior layer.

193. The method for preparing a superficially porous material of claim 191, wherein the prebonding of the substantially nonporous core or sols includes washing with an acid or base, or a charged polyelectrolyte.

194. The method for preparing a superficially porous material of claim 191, wherein the prebonding of the substantially nonporous core or sols includes chemical transformation of an accessible hybrid organic group.

195. The method for preparing a superficially porous material of claim 194, wherein the accessible hybrid organic group is an aromatic group that can undergo sulfonation, nitration, amination, or chloromethylation followed by oxidation or nucleophillic displacement with amine containing groups to form ionizable groups.

196. The method for preparing a superficially porous material of claim 194, where the accessible hybrid organic group is an alkene group that can undergo oxidation, cross-metathesis, or polymerization to form ionizable groups.

197. The method for preparing a superficially porous material of claim 194, where the accessible hybrid organic group is a thiol group that can undergo oxidation, radical addition, nucleophilic displacement, or polymerization to form ionizable groups.

198. The method for preparing a superficially porous material of any one of claims 182-198, wherein the prebonding of the substantially nonporous core or sols includes bonding with an alkoxysilane that has an ionizable group of equation 1,

R(CH₂)_nSi(Y)₃₋

x(R′

)_x 

 

(equation

     1)

where n=1-30, advantageously 2-3;

x is 0-3;

advantageously 0;

Y represents chlorine, dimethylamino, triflate, methoxy, ethoxy, or a longer chain alkoxy group;

R represent a basic group, including (but not limited to) —

NH₂, —

N(R′

)H, —

N(R′

)₂, —

N(R′

)₃⁺, —

NH(CH₂)_mNH₂, —

NH(CH₂)_mN(R′

)H, —

NH(CH₂)_mN(R′

)₂, —

NH(CH₂)_mN(R′

)₃⁺, pyridyl, imidizoyl, polyamine.

R′

independently represents an alkyl, branched alkyl, aryl, or cycloalkyl group;

m is 2-6.

199. The method for preparing a superficially porous material of any one of claims 182-198, wherein the prebonding of the substantially nonporous core or sols includes bonding with an alkoxysilane that has an ionizable group of equation 2,

A(CH₂)_nSi(Y)₃₋

x(R′

)_x 

 

(equation

     2)

where n=1-30, advantageously 2-3;

x is 0-3;

advantageously 0;

Y represents chlorine, dimethylamino, triflate, methoxy, ethoxy, or a longer chain alkoxy group;

A represent an acidic group, including (but not limited to) a sulfonic acid, carboxylic acid, phosphoric acid, boronic acid, arylsulfonic acid, arylcarboxylic acid, arylphosphonic acid, and arylboronic acid.

R′

independently represents an alkyl, branched alkyl, aryl, or cycloalkyl group.

200. The method for preparing a superficially porous material of any one of claims 182-199, wherein each layer of porous shell material is applied using a polyelectrolyte or a chemically degradable polymer.

201. The method of claim 200, wherein the polyelectrolyte or a chemically degradable polymer is removed from the material uses chemical extraction, degradation, or thermal treatment at temperatures less than 600°

C., or combinations thereof.

203. The method for preparing a superficially porous material of claim 201, wherein the alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof, are condensed on the substantially nonporous core in a solution comprising:

ethanol, water, or ammonium hydroxide, or combinations thereof;

an ionic surfactant;

and a non-ionic surfactant.

204. The method for preparing a superficially porous material of claim 203, wherein the ionic surfactant is C₁₀-C₃₀N(R)₃⁺X⁻

, where R is methyl, ethyl, propyl, alkyl, fluoroalkyl;

X is a halogen, hydroxide, or of the form R′

SO₃⁻

or R′

CO₂⁻

where R′

is methyl, ethyl, butyl, propyl, isopropyl, tert-butyl, aryl, tolyl, a haloalkyl or a fluoroalkyl group.

205. The method for preparing a superficially porous material of claim 204, wherein the ionic surfactant is octadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, or dodecyltrimethylammonium chloride.

206. The method for preparing a superficially porous material of any one of claims 182-205, wherein the concentration of ionic surfactant is maintained in the reaction solution between 5-17 mM.

207. The method for preparing a superficially porous material of claim 206, wherein the concentration of ionic surfactant is maintained in the reaction solution between 8-14 mM.

208. The method for preparing a superficially porous material of any one of claims 182-207, wherein the non-ionic surfactant is a diblock or triblock copolymer.

209. The method for preparing a superficially porous material of claim 208, wherein the copolymer is (PEO)x(PPO)y(PEO)x,

wherein

PEO is a polyethylene oxide repeat unit,

PPO is a polypropylene oxide repeat unit,

x is an integer between 5-106,

y is an integer between 30-85,

210. The method for preparing a superficially porous material of claim 209, wherein the triblock copolymer is Pluronic®

P123, having (PEO)₂₀(PPO)₇₀(PEO)₂₀.

211. The method of any one of claims 182-210, wherein the alkoxysilanes, organoalkoxysilanes, or combinations thereof, are condensed on the substantially nonporous core in a solution comprising:

ethanol, water, ammonium hydroxide or combinations thereof;

octadecyltrimethylammonium bromide; and

Pluronic®

P123.

212. The method for preparing a superficially porous material of any one of claims 182-211, wherein the alkoxysilane used is selected from the group of tetramethoxsilane or tetraethoxysilane.

213. The method for preparing a superficially porous material of any one of claims 182-212, wherein the organosiloxane is selected from the group of phenyltriethoxysilane;

phenyltrimethoxysilane;

phenylethyltriethoxysilane;

phenylethyltrimethoxysilane;

ethyltriethoxysilane;

ethyltrimethoxysilane;

methyltriethoxysilane;

methyltrimethoxysilane, diethyldiethoxysilane;

diethyldimethoxysilane 1,4-bis(triethoxysilyl)benzene;

1,4-bis(trimethoxysilyl)benzene;

1,3-bis(triethoxysilyl)benzene;

1,3-bis(trimethoxysilyl)benzene;

1,8-bis(triethoxysilyl)octane;

1,8-bis(trimethoxysilyl)octane;

1,2-bis(trimethoxysilyl)ethane;

2-bis(triethoxysilyl)ethane;

1,2-bis(methyldiethoxysilyl)ethane;

1,2-bis(methyldimethoxysilyl)ethane;

vinyltriethoxysilane;

vinyltrimethoxysilane;

mercaptopropyltrimethoxysilane;

mercaptopropyltriethoxysilane;

1,2-bis(triethoxysilyl)ethene;

1,2-bis(trimethoxysilyl)ethene;

1,1-bis(triethoxysilyl)ethane;

1,1-bis(trimethoxysilyl)ethane;

1,4-bis(triethoxysilylethyl)benzene;

1,4-bis(trimethoxysilylethyl)benzene;

1,3-bis(triethoxysilylethyl)benzene;

or 1,3-bis(trimethoxysilylethyl)benzene.

214. The method for preparing a superficially porous material of any one of claims 182-213, wherein the alkoxysilane used is tetraethoxysilane and the organoalkoxysilane used is 1,2-bis(triethoxysilyl)ethane.

215. The method for preparing a superficially porous material of any one of claims 182-214, wherein the concentration of octadecyltrimethylammonium bromide is maintained between 8-14 mM.

216. The method for preparing a superficially porous material of any one of claims 182-215, wherein the molar ratio of octadecyltrimethylammonium bromide and Pluronic®

P123 is maintained at or above 1.30.

217. The method for preparing a superficially porous material of any one of claims 182-216, wherein the molar ratio of alkoxysilane to organoalkoxysilane ranges between 30:

1 to 1;

30.

218. The method for preparing a superficially porous material of any one of claims 182-217, wherein alkoxysilane, organoalkoxysilane, or combinations thereof are prediluted in ethanol.

219. The method for preparing a superficially porous material of any one of claims 182-218, prediluted ethanol solutions of alkoxysilane, organoalkoxysilane, or combinations thereof are added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.

220. The method for preparing a superficially porous material of any one of claims 182-219, wherein prediluted ethanol solutions of alkoxysilane, organoalkoxysilane, or combinations thereof are added a rate between 5-500 μ

L/min.

221. The method for preparing a superficially porous material of any one of claims 182-220, wherein a secondary solution comprising ethanol, water, ammonium hydroxide, ionic surfactant and non-ionic surfactant is added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.

222. The method for preparing a superficially porous material of any one of claims 182-221, wherein a secondary solution comprising ethanol, water, ammonium hydroxide, ionic surfactant and non-ionic surfactant is added within a range between the rate required to maintain a uniform ratio of particle surface area (m²⁾ to reaction volume, to the rate required to maintain a uniform ratio of particle volume (m³) to reaction volume.

223. The method for preparing a superficially porous material of any one of claims 182-222, wherein the surfactant mixture is removed through one or more of the following;

extractions with acid, water, or organic solvent;

ozonolysis treatments, thermal treatments<

600°

C., or thermal treatments between 500-1200°

C.

224. The method for preparing a superficially porous material of claim 223 wherein the surfactant mixture is removed through combination of acid extractions and ozonolysis treatments.

225. The method for preparing a superficially porous material of any one of claims 182-224, wherein each layer of porous shell material is applied using alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof, comprising the steps of:

a) condensing siloxane precursors on the substantially nonporous core in a reaction mixture comprising ethanol, water or ammonium hydroxide to form a nonporous hybrid inorganic/organic shell material; and

b) introducing porosity through extraction, degradation, oxidation, hydrolysis, deprotection, or transformation of the hybrid group or a combination thereof.

226. The method for preparing a superficially porous material of claim 225, wherein the alkoxysilane used is selected from the group of tetramethoxsilane or tetraethoxysilane.

227. The method for preparing a superficially porous material of claim 226, wherein the organosiloxane is selected as one or more of the following from the group of phenyltriethoxysilane;

phenyltrimethoxysilane;

phenylethyltriethoxysilane;

phenylethyltrimethoxysilane;

ethyltriethoxysilane;

ethyltrimethoxysilane;

methyltriethoxysilane;

methyltrimethoxysilane, diethyldiethoxysilane;

diethyldimethoxysilane 1,4-bis(triethoxysilyl)benzene;

1,4-bis(trimethoxysilyl)benzene;

1,3-bis(triethoxysilyl)benzene;

1,3-bis(trimethoxysilyl)benzene;

1,8-bis(triethoxysilyl)octane;

1,8-bis(trimethoxysilyl)octane;

1,2-bis(trimethoxysilyl)ethane;

1,2-bis(methyldiethoxysilyl)ethane;

1,2-bis(methyldimethoxysilyl)ethane;

vinyltriethoxysilane;

vinyltrimethoxysilane;

mercaptopropyltrimethoxysilane;

mercaptopropyltriethoxysilane;

1,2-bis(triethoxysilyl)ethene;

1,2-bis(trimethoxysilyl)ethene;

1,1-bis(triethoxysilyl)ethane;

1,1-bis(trimethoxysilyl)ethane;

1,4-bis(triethoxysilylethyl)benzene;

1,4-bis(trimethoxysilylethyl)benzene;

1,3-bis(triethoxysilylethyl)benzene;

or 1,3-bis(trimethoxysilylethyl)benzene, octadecyltrimethoxysilane, octadecyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane.

228. The method for preparing a superficially porous material of claim 227, wherein the alkoxysilane used is tetraethoxysilane and the organoalkoxysilane used is octadecyltrimethoxysilane.

229. The method for preparing a superficially porous material of any one of claims 225-228, wherein the alkoxysilane, organoalkoxysilane, or combinations thereof are prediluted in ethanol.

230. The method for preparing a superficially porous material of claim 229, wherein prediluted ethanol solutions of alkoxysilane, organoalkoxysilane, or combinations thereof are added a slow and constant rate to prevent fines generation, aggregation and agglomeration.

231. The method for preparing a superficially porous material of claim 229, wherein prediluted ethanol solutions of alkoxysilane, organoalkoxysilane, or combinations thereof are added a rate between 5-500 L/min.

232. The method for preparing a superficially porous material of any one of claims 225-231, wherein a secondary solution comprising ethanol, water, and ammonium hydroxide is added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.

233. The method for preparing a superficially porous material of claim 235, wherein a secondary solution comprising ethanol, water, and ammonium hydroxide is added within a range between the rate required to maintain a uniform ratio of particle surface area (m²) to reaction volume, to the rate required to maintain a uniform ratio of particle volume (m³) to reaction volume.

234. The method for preparing a superficially porous material of any one of claims 225-233, wherein porosity is introduced through extraction, degradation, hydrolysis, deprotection, or transformation of the hybrid group through one or more of the following;

extractions with acid, water, or organic solvent;

ozonolysis treatments, thermal treatments<

600°

C., or thermal treatments between 500-1200°

C.

235. The method for preparing a superficially porous material of any one of claims 225-234, wherein porosity is introduced through extraction, degradation, hydrolysis, deprotection, or transformation of the hybrid group through combination of acid extractions, ozonolysis treatments and/or thermal treatments<

600°

C.

236. The method for preparing a superficially porous material of any one of claims 182-225, wherein each layer is applied using a mixture of formula XX.

(D)_d(E)_e(F)_f 

 

(Formula XX)

wherein,

a) d+e+f=1

b) D is an inorganic component upon initial condensation.

c) E is a hybrid component upon initial condensation.

d) F is a hybrid component upon initial condensation that can be further reacted to increase the porosity of the superficially porous layer

237. The method for preparing a superficially porous material of claim 236, wherein the precursor for the inorganic component upon initial condensation (D) is selected from oxide, hydroxide, ethoxide, methoxide, propoxide, isopropoxide, butoxide, sec-butoxide, tert-butoxide, iso-butoxide, phenoxide, ethylhexyloxide, 2-methyl-2-butoxide, nonyloxide, isooctyloxide, glycolates, carboxylate, nitrate, chlorides, and mixtures thereof of silicon, titanium, zirconium, or aluminum.

238. The method for preparing a superficially porous material of claim 236, wherein the precursor for the inorganic component upon initial condensation (D) is selected from tetraethoxysilane, tetramethoxysilane, methyl titanium triisopropoxide, methyl titanium triphenoxide, titanium allylacetoacetatetriisopropoxide, titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, and zirconium methacryloxyethylacetoacetate tri-n-propoxide.

239. The method for preparing a superficially porous material of claim 236, wherein the precursor for the hybrid component upon initial condensation (E) is selected from 1,2-bis(triethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,4-bis(triethoxysilyl)benzene, 1,4-bis(trimethoxysilyl)benzene, 1,3-bis(triethoxysilyl)benzene, 1,3-bis(trimethoxysilyl)benzene, 1,3,5-tris(triethoxysilyl)benzene, 1,3,5-tris(trimethoxysilyl)benzene, and bis(4-triethoxysilylphenyl)diethoxysilane.

240. The method for preparing a superficially porous material of claim 236, wherein the precursor for the hybrid component upon initial condensation that can be further reacted to increase the porosity of the superficially porous layer (F) is selected from phenyltrimethoxysilane, phenyltriethoxysilane, acetyloxyethyltrimethoxysilane;

acetyloxyethyltriethoxysilane;

chloroethyltriethoxysilane;

chloroethyltrimethoxysilane;

methacryloxypropyltrimethoxysilane;

methacryloxypropyltriethoxysilane;

bromoethyltrimethoxysilane;

bromoethyltriethoxysilane;

fluorotriethoxysilane;

fluorotrimethoxysilane; and

alkoxysilanes of the type;

(CH₃CH₂O)<sub>4−

v</sub>Si(OR*)_v 

 

(Formula XXb)

wherein

R* was the corresponding octadecyl, dodecyl, octyl, 2-ethoxyethyl, or 3-ethyl-3-pentyl group,

v was an integer equal to 1-4, 241. The method for preparing a superficially porous material of claim 236, wherein porosity is introduced by reaction of hybrid group F through protodesilylation, hydrolysis, deprotection, acid extraction, thermal treatment<

600°

C., oxidation, ozonolysis or decomposition.

242. The method for preparing a superficially porous material of any one of claims 182-241, where the 1-50 layers are formed in the process

243. The method for preparing a superficially porous material of claim 242, wherein 2-5 layers are formed.

244. The method for preparing a superficially porous material of claim 243, wherein 1-2 layers are formed.

245. The method for preparing a superficially porous material of any one of claims 182-244, wherein the superficially porous material is optimized by acid extraction, classification, ozonolysis treatment, hydrothermal treatment, acid treatment or combinations thereof.

246. A method for increasing the porosity of a substantially nonporous material comprising:

a.) providing a substantially nonporous core material; and

b.) applying to said core material one or more layers of porous shell material to form a superficially porous material.

247. The method for increasing the porosity of a substantially nonporous material of claim 246, wherein each layer of porous shell material is independently selected from a porous inorganic/organic hybrid material, a porous silica, a porous composite material or mixtures thereof.