Reactive membrane for filtration and purification of gases of impurities and method utilizing the same

• US 5,637,544 A
• Filed: 02/19/1995
• Issued: 06/10/1997
• Est. Priority Date: 06/06/1991
• Status: Expired due to Fees

• Current Assignee: Arizona Board of Regents (University of Arizona)
• Original Assignee: Arizona Board of Regents (University of Arizona)
• Inventors: Shadman, Farhang F.
• Primary Examiner(s): Langel, Wayne
• Assistant Examiner(s): Dunn, Jr., Thomas G.
• Application Number:
  US08/375,257
• Time in Patent Office: 842 Days
• Field of Search: 502/4, 502/413, 502/415, 502/416, 502/417, 427/249, 427/245, 427/255.7, 427/255, 427/244, 264/29.5
• US Class Current: 502/4
• CPC Class Codes: B01D 2323/36 Introduction of specific chemical groups
• CPC Class Codes: B01D 2325/12 Adsorbents being present on the surface of the membranes or in the pores
• CPC Class Codes: B01D 53/22 by diffusion manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 53/268 by diffusion
• CPC Class Codes: B01D 53/28 Selection of materials for use as drying agents
• CPC Class Codes: B01D 67/0072 by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/1214 Chemically bonded layers, e.g. cross-linking
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 71/02 Inorganic material
• CPC Class Codes: B01D 71/021 Carbon
• CPC Class Codes: B01D 71/05 Cermet materials
• CPC Class Codes: B01J 12/007 in the presence of catalytically active bodies, e.g. porous plates
• CPC Class Codes: B01J 20/28023 Fibres or filaments fibres or filaments in the form of membranes B01J20/28038; B01J20/28007 takes precedence
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/28085 being more than 50 nm, i.e. macropores
• 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

Abstract

A reactive membrane for removing impurities, such as water, oxygen and organic compounds, from a gas is provided. The reactive membrane includes a porous inorganic substrate having exposed surfaces and at least one carbon layer, which is modified to present active sites, deposited on the exposed surfaces. The active sites include metal species which are at least partially deoxygenated and are chemically bonded to the carbon layer. Methods of forming the reactive membrane and of removing impurities from a gas with the membrane are also provided.

Claims

1. A reactive membrane for removing impurities from a gas comprising:

(a) a porous inorganic substrate; and

(b) at least one carbon layer deposited on substantially all of the porous inorganic substrate, the carbon layer being modified to present active sites which include at least partially deoxygenated metal species selected from the group consisting of manganese, magnesium, the alkali metals and mixtures thereof, wherein the metal species is chemically bonded to the carbon layer and serves as a scavenger, interacting with impurities and removing them from the gas.

2. A reactive membrane as claimed in claim 1 wherein the at least one carbon layer is deposited directly on exposed surfaces of the porous substrate.

3. The reactive membrane of claim 1 wherein the porous inorganic substrate comprises porous carbon.

4. The reactive membrane of claim 1 wherein the porous inorganic substrate comprises a porous ceramic material.

5. The reactive membrane of claim 1 wherein the porous inorganic substrate comprises a porous metal.

6. The reactive membrane of claim 5 wherein, the porous metal substrate has a pore size in the range from about 2 to about 5 microns.

7. The reactive membrane of claim 5 wherein the porous metal includes sintered stainless steel and has an initial pore size before deposition of the carbon layer in the range from about 2 microns to about 5 microns, wherein the carbon layer has a thickness greater than about 20 Å

, and wherein the active sites include substantially deoxygenated alkali metal species chemically bonded to the carbon layer.

8. The reactive membrane of claim 7 wherein the alkali metal species includes sodium.

9. The reactive membrane of claim 5 wherein the active sites include substantially deoxygenated alkali metal species.

10. The reactive membrane of claim 9 wherein the porous metal includes stainless steel and the alkali metal species includes sodium.

11. The reactive membrane of claim 9 wherein the porous metal includes stainless steel and the alkali metal species includes potassium.

12. The reactive membrane according to claim 5 which includes first and second carbon layers deposited on substantially all of the porous metal substrate.

13. The reactive membrane according to claim 12 wherein the active sites on the carbon layers include at least two metal species.

14. The reactive membrane of claim 1 wherein the carbon layer has a thickness greater than about 20 Å

.

15. The reactive membrane of claim 14 wherein the carbon layer has a thickness of about 20 Å

to about 100 Å

.

16. The reactive membrane of claim 1 wherein the porous inorganic substrate includes an α

-alumina membrane coated with a monolayer of γ

-alumina, a carbon layer which has a thickness of about 20 Å

to about 100 Å

, and the active sites include substantially deoxygenated alkali metal species chemically bonded to the carbon layer.

17. The reactive membrane of claim 1 wherein the metal species includes manganese.

18. The reactive membrane of claim 1 wherein the metal species includes magnesium.

19. The reactive membrane of claim 1 wherein the metal species includes an alkali metal species.

20. The reactive membrane of claim 19 wherein the alkali metal species includes sodium.

21. The reactive membrane of claim 19 wherein the alkali metal species includes potassium.

22. The reactive membrane according to claim 1 wherein the active sites include substantially deoxygenated alkali metal species ionically bonded to the carbon layer.

23. The reactive membrane according to claim 1 wherein the porous inorganic substrate comprises porous metal, a porous ceramic material or porous carbon.

24. The reactive membrane according to claim 23 wherein the porous metal includes stainless steel.

25. The reactive membrane according to claim 24 wherein the porous metal includes sintered stainless steel powder or sintered stainless steel fibers.

26. The reactive membrane according to claim 23 wherein the porous ceramic material includes an α

-alumina membrane coated with a monolayer of γ

-alumina.

27. The reactive membrane according to claim 23 wherein the porous inorganic substrate comprises a porous ceramic material which includes about 0.1 to 1% of a metallic impurity.

28. The reactive membrane according to claim 27 wherein the metallic impurity comprises iron or nickel.

29. The reactive membrane according to claim 1 wherein the metal species include manganese, magnesium, lithium, sodium or potassium species.

30. The reactive membrane according to claim 1 wherein the porous inorganic substrate comprises a porous ceramic material and the carbon layer has a thickness of about 20Å

to about 100Å

.

31. The reactive membrane according to claim 1 wherein the porous inorganic substrate comprises a porous ceramic material which has an initial pore size of about 500Å

.

32. The reactive membrane according to claim 31 wherein the porous ceramic material has a reduced pore size of about 50Å

to about 200Å

.

33. The reactive membrane according to claim 1 comprising a porous 316L stainless steel substrate having an initial pore size of about 4 microns and the active sites include substantially deoxygenated sodium species chemically bonded to the carbon layer.

34. The reactive membrane according to claim 1 which includes first and second carbon layers deposited on substantially all of the porous inorganic substrate.

35. The reactive membrane according to claim 34 wherein the active sites on the carbon layers include at least two metal species.

36. The reactive membrane according to claim 35 wherein the first carbon layer is modified to present active sites which include at least partially deoxygenated first metal species chemically bonded to the first carbon layer and the second carbon layer is modified to present active sites which include at least partially deoxygenated second metal species chemically bonded to the second carbon layer.

146. The reactive membrane according to claim 1 wherein the active sites include metal species ionically bonded to the carbon layer.

37. A method for forming a reactive membrane for removing homogeneous and heterogeneous impurities from gases, said method comprising:

(a) depositing at least one layer of carbon on substantially all of a porous inorganic substrate;

(b) depositing a precursor metal species on the carbon layer, thereby forming a membrane; and

(c) then heating the membrane to form active sites on the carbon layer, thereby forming a reactive membrane, wherein the active sites include at least partially deoxygenated metal species selected from the group consisting of manganese, magnesium, the alkali metals and mixtures thereof, and wherein the metal species is chemically bonded to the carbon layer and serves as a scavenger, interacting with impurities and removing them from the gas.

38. The method for forming a reactive membrane as claimed in claim 37 wherein the step of depositing the carbon layer includes depositing the at least one layer of carbon directly on exposed surfaces of the porous inorganic substrate.

39. The method of claim 37 wherein depositing the carbon layer includes depositing the carbon on a porous ceramic substrate.

40. The method of claim 37 wherein depositing the carbon layer includes depositing the carbon on a porous metal substrate.

41. The method of claim 37 wherein depositing the carbon layer includes disproportionating carbon monoxide vapor.

42. The method of claim 41 wherein the carbon monoxide vapor contains hydrogen.

43. The method of claim 42 wherein the carbon monoxide vapor contains less than about 15% hydrogen by volume.

44. The method of claim 37 wherein depositing the carbon layer includes disproportionating hydrocarbon vapor.

45. The method of claim 44 wherein the hydrocarbon vapor contains hydrogen.

46. The method of claim 45 wherein the hydrocarbon vapor contains less than about 15% hydrogen by volume.

47. The method of claim 37 wherein depositing the carbon layer includes depositing the carbon layer from a hydrogen-containing vapor.

48. The method of claim 47 wherein the hydrogen-containing vapor includes less than about 15% hydrogen by volume.

49. The method of claim 37 wherein depositing a precursor metal species on the carbon layer comprises contacting the carbon layer with a mixture including the precursor metal species.

50. The method of claim 49 wherein the mixture is a solution or a slurry of the precursor metal species.

51. The method of claim 49 wherein contacting the carbon layer with a precursor metal species comprises contacting the carbon layer with a precursor metal species in an aqueous solvent.

52. The method of claim 51 wherein the precursor metal species includes metal hydroxide species.

53. The method of claim 52 wherein the metal hydroxide species includes an alkali metal hydroxide species.

54. The method of claim 51 wherein the precursor metal species includes metal oxalate species.

55. The method of claim 54 wherein the metal oxalate includes manganese oxalate.

56. The method of claim 51 further comprising removing the aqueous solvent from the porous inorganic substrate prior to heating the porous inorganic substrate to form active sites.

57. The method of claim 49 wherein contacting the carbon layer with a precursor metal species comprises contacting the carbon layer with a precursor metal species in a non-aqueous solvent.

58. The method of claim 57 wherein the non-aqueous solvent includes anhydrous ammonia.

59. The method of claim 57 wherein the precursor metal species includes alkali metal species.

60. The method of claim 57 wherein the precurser metal species includes sodium and the non-aqueous solvent includes anhydrous ammonia.

61. The method of claim 37 wherein heating to form active sites comprises heating to greater than about 300°

C. in an inert atmosphere for a period of time greater than about 1 hour.

62. The method of claim 37 wherein heating to form active sites comprises heating to greater than about 300°

C. in a reducing atmosphere for a period of time greater than about 1 hour.

63. The method of claim 62 wherein the reducing atmosphere contains hydrogen.

64. The method of claim 63 wherein the reducing atmosphere contains greater than about 1% hydrogen by volume.

65. The method of claim 37 wherein heating to form active sites includes substantially deoxygenating the metal species to form the active sites.

66. The method of claim 37 wherein:

(a) depositing at least one layer of carbon on a porous inorganic substrate includes disproportionating carbon monoxide vapor containing hydrogen;

(b) depositing a precursor metal species includes contacting the carbon layer with a vapor of the metal species; and

(c) heating the porous inorganic substrate includes heating the carbon layer to greater than about 300°

C. in a hydrogen-containing atmosphere to form active sites including substantially deoxygenated metal species.

67. The method of claim 37 wherein:

(a) depositing at least one layer of carbon on a porous inorganic substrate includes disproportionating carbon monoxide vapor containing hydrogen;

(b) depositing a precursor metal species includes contacting the carbon layer with a mixture of the metal species in anhydrous ammonia; and

(c) heating the porous inorganic substrate includes heating the carbon layer to greater than about 300°

C. in a hydrogen-containing atmosphere to form active sites including substantially deoxygenated metal species.

68. The method of claim 67 wherein the precursor metal species includes alkali metal species.

69. The method of claim 68 wherein the alkali metal species includes sodium.

70. The method of claim 68 wherein the alkali metal species includes potassium.

71. The method of claim 68 wherein depositing at least one layer of carbon includes disproportionating carbon monoxide vapor containing hydrogen on a porous metal substrate.

72. The method of claim 71 wherein the porous metal substrate is a sintered porous metal fiber or powder.

73. The method of claim 72 wherein heating to form active sites includes heating for a period of time greater than about 1 hour.

74. The method of claim 73 wherein heating the carbon layer to form active sites includes heating in an atmosphere containing about 2% to about 35% hydrogen by volume.

75. The method of claim 37 wherein depositing the precursor metal species on the carbon layer comprises forming a vapor of the precursor metal species and contacting the vapor with the carbon layer.

76. The method of claim 75 wherein the vapor of the precursor metal species comprises a vapor of a metal, metal oxide or metal hydroxide.

77. The method of claim 76 wherein the vapor of the precursor metal species comprises a vapor of a metal hydroxide species.

78. The method of claim 77 wherein the vapor of the metal hydroxide species comprises a vapor of an alkali metal hydroxide species.

79. The method of claim 37 wherein depositing a precursor metal species on the carbon layer comprises contacting the carbon-coated substrate with a precursor metal species dissolved in a solvent.

80. The method of claim 79 wherein the solvent is water.

81. The method of claim 79 wherein the solvent is a non-aqueous solvent.

82. The method of claim 81 wherein the non-aqueous solvent is anhydrous ammonia.

83. The method of claim 81 further comprising the step of purging the porous inorganic substrate with an inert gas to remove the non-aqueous solvent prior to heating the porous inorganic substrate to form the active sites.

84. The method of claim 37 wherein depositing a precursor metal species on the carbon layer comprises contacting the carbon-coated substrate with a precursor metal species slurried in a solvent.

85. The method of claim 37 wherein depositing at least one layer of carbon comprises disproportionating carbon monoxide to carbon while in contact with the porous inorganic substrate.

86. The method of claim 37 wherein heating the porous inorganic substrate to form active sites comprises heating the porous inorganic substrate to greater than about 300°

C. in an inert atmosphere.

87. The method of claim 37 wherein heating the porous inorganic substrate to form active sites comprises heating the porous inorganic substrate to greater than about 300°

C. in a hydrogen-containing atmosphere.

88. A reactive membrane for removing impurities from a gas comprising:

(a) a porous metal substrate; and

(b) at least one carbon layer deposited on the porous metal substrate, the carbon layer being modified to present active sites which include at least partially deoxygenated metal species selected from the group consisting of manganese, magnesium, the alkali metals and mixtures thereof, wherein the metal species is chemically bonded to the carbon layer and serves as a scavenger, interacting with impurities and removing them from the gas.

89. The reactive membrane as claimed in claim 88 wherein the at least one carbon layer is deposited directly on exposed surfaces of the porous metal substrate.

90. The reactive membrane of claim 88 wherein the metal species includes manganese.

91. The reactive membrane of claim 90 wherein the porous metal substrate includes sintered metal fibers or powder, the carbon layer has a thickness greater than about 20 Å

thick and coats substantially all of the surface area of the porous metal substrate, and the manganese is substantially deoxygenated.

92. The reactive membrane of claim 91 wherein the sintered metal includes stainless steel and the porous metal substrate has an initial pore size before deposition of the carbon layer in the range from about 2 microns to about 5 microns.

93. The reactive membrane of claim 88 wherein the metal species includes magnesium.

94. The reactive membrane of claim 93 wherein the porous metal substrate includes sintered metal fibers or powder, the carbon layer has a thickness greater than about 20 Å

and coats substantially all of the surface area of the porous metal substrate, and the magnesium is substantially deoxygenated.

95. The reactive membrane of claim 94 wherein the sintered metal includes stainless steel and the porous metal substrate has a pore size in the range from about 2 microns to about 5 microns.

96. The reactive membrane of claim 88 wherein the metal species includes sodium.

97. The reactive membrane of claim 96 wherein the porous metal substrate includes sintered metal fibers or powder, the carbon layer has a thickness greater than about 20 Å

and coats substantially all of the surface area of the porous metal substrate, and the sodium is substantially deoxygenated.

98. The reactive membrane of claim 97 wherein the sintered metal includes stainless steel and the porous metal substrate has a pore size in the range from about 2 microns to about 5 microns.

99. The reactive membrane of claim 88 wherein the metal species includes potassium.

100. The reactive membrane of claim 99 wherein the porous metal substrate includes sintered metal fibers or powder, the carbon layer has a thickness greater than about 20 Å

and coats substantially all of the surface area of the porous metal substrate, and the potassium is substantially deoxygenated.

101. The reactive membrane of claim 100 wherein the sintered metal includes stainless steel and the porous metal substrate has an initial pore size before deposition of the carbon layer in the range from about 2 microns to about 5 microns.

102. A method for forming a reactive membrane for removing homogeneous and heterogeneous impurities from gases, said method comprising:

(a) depositing at least one layer of carbon on a porous metal substrate;

(b) depositing a precursor metal species on the carbon layers, thereby forming a membrane; and

(c) heating the membrane to form active sites on the carbon layer, thereby forming a reactive membrane, wherein the active sites include at least partially deoxygenated metal species selected from the group consisting of manganese, magnesium, the alkali metals and mixtures thereof, and wherein the metal species is chemically bonded to the carbon layer and serves as a scavenger, interacting with impurities and removing them from the gas.

103. The method for forming a reactive membrane as claimed in claim 102 wherein the step of depositing the carbon layer includes depositing the at least one layer of carbon directly on exposed surfaces of the porous metal substrate.

104. The method of claim 102 wherein depositing the carbon layer on the porous metal substrate includes depositing carbon on substantially all of the exposed surfaces of the porous metal substrate.

105. The method of claim 102 wherein:

(a) depositing at least one layer of carbon includes depositing carbon on a sintered porous metal substrate;

(b) depositing the precursor metal species on the carbon layer includes contacting the carbon layer with an aqueous mixture including manganese oxalate; and

(c) heating the porous metal substrate includes heating to greater than about 300°

C. in a hydrogen-containing atmosphere to form active sites including substantially deoxygenated manganese species.

106. The method of claim 105 wherein the sintered metal includes sintered stainless steel fibers or powders.

107. The method of claim 102 wherein:

(a) depositing at least one layer of carbon includes depositing carbon on a sintered porous metal substrate;

(b) depositing the precursor metal species on the carbon layer includes contacting the carbon layer with a mixture including magnesium; and

(c) heating the porous metal substrate includes heating to greater than about 300°

C. in a hydrogen-containing atmosphere to form active sites including substantially deoxygenated magnesium species.

108. The method of claim 107 wherein the sintered metal substrate includes sintered stainless steel fibers or powders.

109. The method of claim 102 wherein:

(a) depositing at least one layer of carbon includes depositing carbon on a sintered porous metal substrate;

(b) depositing the precursor metal species on the carbon layer includes contacting the carbon layer with an aqueous mixture including alkali metal species; and

(c) heating the porous metal substrate includes heating to greater than about 300°

C. in a hydrogen-containing atmosphere to form active sites including substantially deoxygenated alkali metal species.

110. The method of claim 109 wherein the sintered metal substrate includes sintered stainless steel fibers or powders.

111. The method of claim 110 wherein the alkali metal species includes sodium.

112. The method of claim 110 wherein the alkali metal species includes potassium.

113. The method of claim 102 wherein:

(a) depositing at least one layer of carbon includes depositing carbon on a sintered porous metal substrate;

(b) depositing the precursor metal species on the carbon layer includes contacting the carbon layer with a non-aqueous mixture including alkali metal species; and

(c) heating the porous metal substrate includes heating to greater than about 300°

C. in a hydrogen-containing atmosphere to form active sites including substantially deoxygenated alkali metal species.

114. The method of claim 113 wherein the sintered metal substrate includes sintered stainless steel fibers or powders.

115. The method of claim 114 wherein the alkali metal species includes sodium.

116. The method of claim 114 wherein the alkali metal species includes potassium.

117. The method of claim 113 wherein the non-aqueous mixture includes anhydrous ammonia.

118. The method of claim 102 wherein:

(a) depositing at least one layer of carbon includes depositing carbon a sintered porous metal substrate;

(b) depositing the precursor metal species on the carbon layer includes contacting the carbon layer with a vapor of the metal species; and

(c) heating the porous metal substrate includes heating to greater than about 300°

C. in a hydrogen-containing atmosphere to form active sites including substantially deoxygenated metal species.

119. The method of claim 118 wherein the sintered metal substrate includes sintered stainless steel fibers or powders.

120. The method of claim 119 wherein the vapor of the precursor metal species comprises a vapor of a metal, metal oxide, or metal hydroxide species.

121. The method of claim 120 wherein the vapor of the precursor metal species comprises a vapor of an alkali metal hydroxide species.

132. The method of claim 121 wherein heating the carbon-coated substrate includes heating the carbon-coated substrate in a hydrogen-containing atmosphere.

133. The method of claim 132 wherein heating in a hydrogen-containing atmosphere comprises heating in an atmosphere which comprises greater than about 1% hydrogen by volume.

134. The method of claim 132 wherein heating in a hydrogen-containing atmosphere comprises heating in an atmosphere which comprises from about 2% to about 35% hydrogen by volume.

135. The method of claim 132 wherein heating in a hydrogen-containing atmosphere comprises heating in an atmosphere which comprises from about 4% to about 10% hydrogen by volume.

136. The method of claim 132 wherein the hydrogen-containing atmosphere comprises an inert gas.

137. The method of claim 136 wherein the inert gas includes nitrogen, argon, or helium.

122. A method for forming a reactive membrane for removing homogeneous and heterogeneous impurities from gases, said method comprising:

(a) depositing at least one layer of carbon on a porous inorganic substrate;

(b) forming a membrane including the porous inorganic substrate, the at least one carbon layer, and a precursor metal species, the at least one carbon layer positioned between the substrate and the precursor metal species, the precursor metal species being deposited on the carbon layer by contacting the carbon layer with the precursor metal species in a non-aqueous solvent; and

(c) heating the membrane to form active sites on the carbon layer including at least partially deoxygenated metal species selected from the group consisting of manganese, magnesium, the alkali metals and mixtures thereof, thereby forming a reactive membrane, wherein the metal species is chemically bonded to the carbon layer and serves as a scavenger, interacting with impurities and removing them from the gas.

123. The method for forming a reactive membrane as claimed in claim 122 wherein the step of depositing the carbon layer includes depositing the at least one layer of carbon directly on exposed surfaces of the porous inorganic substrate.

124. The method of claim 122 wherein depositing the carbon layer on the porous inorganic substrate includes depositing on substantially all of the exposed surfaces of.

125. The method of claim 122 wherein the non-aqueous solvent includes anhydrous ammonia.

126. The method of claim 122 wherein depositing a precursor metal species includes contacting the carbon layer with a mixture including an alkali metal species in anhydrous ammonia and heating the carbon layer includes heating to greater than 300°

C. in a hydrogen-containing atmosphere to form active sites including substantially deoxygenated alkali metal species.

127. The method of claim 126 wherein the alkali metal species includes sodium.

128. The method of claim 126 wherein the alkali metal species includes potassium.

129. The method of claim 122 further comprising removing the anhydrous ammonia including purging the porous inorganic substrate with an inert gas.

130. The method of claim 129 wherein removing the anhydrous ammonia further includes gradually heating to greater than about 110°

C.

131. A method for activating a reactive membrane comprising heating to greater than about 300°

C. in a reducing atmosphere a porous inorganic substrate which includes a carbon layer having sites comprising metal species selected from the group consisting of manganese, magnesium, and the alkali metals and chemically bonded to the carbon layer, and activating the sites by at least partially deoxygenating the metal species whereby the metal species serve as a scavenger, interacting with impurities in a gas and removing the impurities from the gas.

138. The method of claim 131 wherein heating the substrate comprises heating to greater than about 380°

C. in a reducing atmosphere.

139. The method of claim 131 wherein heating the substrate comprises heating to greater than about 500°

C. in a reducing atmosphere.

140. The method of claim 131 wherein activating the sites includes substantially deoxygenating the metal species.

141. The method of claim 131 wherein heating the substrate includes heating for a period of time greater than about 1 hour.

142. The method of claim 141 wherein the period of time is greater than about 12 hours.

143. The method of claim 131 wherein heating the carbon-coated substrate comprises heating to greater than about 500°

C. in an atmosphere which comprises greater than about 1% hydrogen by volume for greater than about 1 hour and activating the sites includes substantially deoxygenating the metal species.

144. The method of claim 143 wherein the atmosphere comprises from about 2% to about 35% hydrogen by volume and the balance comprises an inert gas.

145. The method of claim 144 wherein the atmosphere comprises from about 4% to about 10% hydrogen by volume and the inert gas includes nitrogen, argon, or helium.