Process for purifying single-wall carbon nanotubes and compositions thereof
First Claim
Patent Images
1. A method for purifying single-wall carbon nanotubes comprising the steps of:
- (a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere;
(b) adding water vapor to the oxidizing gaseous atmosphere; and
(c) treating the single-wall carbon nanotube material with a solution comprising a halogen-containing acid.
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Abstract
The present invention relates to a process for the purification of single-wall carbon nanotubes and the purified single-wall carbon nanotube material. Known methods of single-wall carbon nanotube production result in a single-wall carbon nanotube product that contains single-wall carbon nanotubes in addition to impurities including residual metal catalyst particles and amounts of small amorphous carbon sheets that surround the catalyst particles and appear on the sides of the single-wall carbon nanotubes and “ropes” of single-wall carbon nanotubes. The purification process removes the extraneous carbon as well as metal-containing residual catalyst particles. The process employs steps including a gas-phase oxidation of the amorphous carbon and subsequent liquid-phase reaction of a halogen-containing acid with the metal-containing species. Optionally, the single-wall carbon nanotube material may be annealed dry or in the presence of moisture. The present invention provides a scalable means for producing high-purity single-wall carbon nanotube material.
140 Citations
206 Claims
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1. A method for purifying single-wall carbon nanotubes comprising the steps of:
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(a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere;
(b) adding water vapor to the oxidizing gaseous atmosphere; and
(c) treating the single-wall carbon nanotube material with a solution comprising a halogen-containing acid. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 201, 202, 203, 204, 205, 206)
(a) performing a second oxidizing of the single-wall carbon nanotube material after the treating step, wherein the second oxidizing step is performed utilizing a gaseous atmosphere selected from the group consisting of the oxidizing gaseous atmosphere and a different oxidizing gaseous atmosphere than the oxidizing gaseous atmosphere; and
(b) performing a second treating of the single-wall carbon nanotube material after the second oxidizing step, wherein the second treating step is performed utilizing an acid solution selected from the group consisting of the solution comprising the halogen-containing acid, a first different solution comprising the halogen-containing acid, and a second different solution comprising a different halogen-containing acid.
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22. The method of claim 21 wherein the second oxidizing step is performed at the same temperature as the oxidizing step.
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24. The method of claim 1 further comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material.
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25. The method of claim 24, wherein the amorphous carbon is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
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26. The method of claim 24, wherein the amorphous carbon is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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27. The method of claim 24, wherein the amorphous carbon is present in an amount at most about 0.2 wt % of the purified single-wall carbon nanotube material.
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28. The method of claim 24, wherein
(a) the metallic impurity comprises metal; - and
(b) the metal is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
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29. The method of claim 28, wherein the metal is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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30. The method of claim 28, wherein the metal is present in an amount at most about 0.1 wt % of the purified single-wall carbon nanotube material.
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31. The method of claim 24, wherein the recovering step comprises filtration.
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32. The method of claim 24, wherein the recovering step comprises washing the single-wall carbon nanotube material with water.
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33. The method of claim 24, wherein the recovering step comprises washing the single-wall carbon nanotube material with methanol.
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34. The method of claim 24, wherein the recovering step comprises drying the single-wall carbon nanotube material.
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35. The method of claim 24, wherein the drying step is performed in a vacuum.
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36. The method of claim 1 further comprising annealing the single-wall carbon nanotube material.
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201. The method of claim 21, wherein the second oxidizing step is performed at a temperature higher than the oxidizing step.
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202. The method of claim 36, wherein:
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(a) the annealing step is performed at a temperature between about 600°
C. and about 1000°
C.; and
(b) the annealing step utilizes an annealing gas mixture comprising a gas selected from the group consisting of inert gases, nitrogen, carbon dioxide, and combinations thereof.
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203. The method of claim 202, wherein the annealing gas mixture further comprises water vapor.
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204. The method of claim 1 further comprising reduction of the single-wall carbon nanotube material.
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205. The method of claim 204, wherein the reduction step is performed at a temperature between about 250°
- C. and about 500°
C.
- C. and about 500°
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206. The method of claim 204, wherein the reduction step is performed with a gas comprising hydrogen gas.
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23. A method for purifying single-wall carbon nanotubes comprising the steps of:
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(a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere;
(b) treating the single-wall carbon nanotube material with a solution comprising a halogen-containing acid;
(c) performing a second oxidizing of the single-wall carbon nanotube material after the treating step, wherein the second oxidizing step is performed utilizing a gaseous atmosphere selected from the group consisting of the oxidizing gaseous atmosphere and a different oxidizing gaseous atmosphere than the oxidizing gaseous atmosphere, wherein the second oxidizing step is performed at a temperature higher than the oxidizing step; and
(d) performing a second treating of the single-wall carbon nanotube material after the second oxidizing step, wherein the second treating step is performed utilizing an acid solution selected from the group consisting of the solution comprising the halogen-containing acid, a first different solution comprising the halogen-containing acid, and a second different solution comprising a different halogen-containing acid.
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37. A method for purifying single-wall carbon nanotubes comprising the steps of:
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(a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere;
(b) treating the single-wall carbon nanotube material with a solution comprising a halogen-containing acid and (c) annealing the single-wall carbon nanotube material, wherein;
(i) the annealing step is performed at a temperature between about 600°
C. and about 1000°
C.; and
(ii) the annealing step utilizes an annealing gas mixture comprising a gas selected from the group consisting of inert gases, nitrogen, carbon dioxide, and combinations thereof. - View Dependent Claims (38, 39)
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40. A method for purifying single-wall carbon nanotubes comprising the steps of:
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(a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere;
(b) reduction of the single-wall carbon nanotube material; and
(c) treating the single-wall carbon nanotube material with a solution comprising a halogen-containing acid. - View Dependent Claims (41, 42, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200)
(a) performing a second oxidizing of the single-wall carbon nanotube material after the treating step, wherein the second oxidizing step is performed utilizing a gaseous atmosphere selected from the group consisting of the oxidizing gaseous atmosphere and a different oxidizing gaseous atmosphere than the oxidizing gaseous atmosphere; and
(b) performing a second treating of the single-wall carbon nanotube material after the second oxidizing step, wherein the second treating step is performed utilizing an acid solution selected from the group consisting of the solution comprising the halogen-containing acid, a first different solution comprising the halogen-containing acid, and a second different solution comprising a different halogen-containing acid.
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183. The method of claim 182 wherein the second oxidizing step is performed at the same temperature as the oxidizing step.
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184. The method of claim 182 wherein the second oxidizing step is performed at a temperature higher than the oxidizing step.
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185. The method of claim 40 further comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material.
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186. The method of claim 185, wherein the amorphous carbon is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
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187. The method of claim 185, wherein the amorphous carbon is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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188. The method of claim 185, wherein the amorphous carbon is present in an amount at most about 0.2 wt % of the purified single-wall carbon nanotube material.
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189. The method of claim 185, wherein
(a) the metallic impurity comprises metal; - and
(b) the metal is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
- and
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190. The method of claim 189, wherein the metal is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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191. The method of claim 189, wherein the metal is present in an amount at most about 0.1 wt % of the purified single-wall carbon nanotube material.
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192. The method of claim 189, wherein the recovering step comprises filtration.
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193. The method of claim 185, wherein the recovering step comprises washing the single-wall carbon nanotube material with water.
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194. The method of claim 185, wherein the recovering step comprises washing the single-wall carbon nanotube material with methanol.
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195. The method of claim 185, wherein the recovering step comprises drying the single-wall carbon nanotube material.
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196. The method of claim 195, wherein the drying step is performed in a vacuum.
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197. The method of claim 40 further comprising annealing the single-wall carbon nanotube material.
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198. The method of claim 40, wherein:
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(a) the annealing step is performed at a temperature between about 600°
C. and about 1000°
C.; and
(b) the annealing step utilizes an annealing gas mixture comprising a gas selected from the group consisting of inert gases, nitrogen, carbon dioxide, and combinations thereof.
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199. The method of claim 198, wherein the annealing gas mixture further comprises water vapor.
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200. The method of claim 197, wherein the annealing step is performed in a vacuum.
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43. A method for purifying single-wall carbon nanotubes comprising the steps of:
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(a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere at a temperature between about 200°
C. and about 500°
C.;
(b) reoxidizing the single-wall carbon nanotube material at a temperature higher than the oxidizing step; and
(c) treating the single-wall carbon nanotube material with an aqueous solution comprising HCl. - View Dependent Claims (44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76)
(a) performing a second oxidizing of the single-wall carbon nanotube material after the treating step, wherein the second oxidizing step is performed utilizing a gaseous atmosphere selected from the group consisting of the oxidizing gaseous atmosphere and a different oxidizing gaseous atmosphere than the oxidizing gaseous atmosphere;
(b) performing a second reoxidizing step of the single-wall carbon nanotube material after the second oxidizing step, wherein the second reoxidizing step is performed at a higher temperature than the second oxidizing step; and
(c) performing a second treating of the single-wall carbon nanotube material after the second reoxidizing step, wherein the second treating step is performed utilizing an acid solution selected from the group consisting of the solution comprising the halogen-containing acid, a first different solution comprising the halogen-containing acid, and a second different solution comprising a different halogen-containing acid.
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54. The method of claim 53, wherein the second oxidizing step is performed at a higher temperature than the first oxidizing step.
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55. The method of claim 54, wherein the temperature of the second oxidizing step is at most about 500°
- C.
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56. The method of claim 43, wherein the concentration of the HCl is present in an amount at least about 9 wt % of the aqueous solution.
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57. The method of claim 44, herein the concentration of the HCl is present in an amount between about 9 wt % and about 38 wt % of the aqueous solution.
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58. The method of claim 43 further comprising filtering the single-wall carbon nanotube material.
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59. The method of claim 43 further comprising washing the single-wall carbon nanotube material.
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60. The method of claim 59, wherein the washing step is performed with methanol.
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61. The method of claim 59, the washing step is performed with water.
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62. The method of claim 43 further comprising drying the single-wall carbon nanotube material.
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63. The method of claim 62, wherein the drying step comprises vacuum drying.
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64. The method of claim 62 further comprising heating the single-wall carbon nanotube material in a gaseous mixture comprising carbon dioxide and water vapor after the drying step.
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65. The method of claim 64, wherein the heating step is performed at a temperature at most about 800°
- C.
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66. The method of claim 43, further comprising annealing the single-wall carbon nanotube material in a gaseous atmosphere comprising an inert gas.
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67. The method of claim 66, wherein the inert gas comprises argon.
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68. The method of claim 43 further comprising annealing the single-wall carbon nanotube material in a gaseous atmosphere comprising nitrogen.
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69. The method of claim 66, wherein the gaseous atmosphere comprises water vapor.
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70. The method of claim 43 further comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material.
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71. The method of claim 70, wherein the amorphous carbon is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
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72. The method of claim 70, wherein the amorphous carbon is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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73. The method of claim 70, wherein the amorphous carbon is present in an amount at most about 0.2 wt % of the purified single-wall carbon nanotube material.
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74. The method of claim 70, wherein
(a) the metallic impurity comprises metal; - and
(b) the metal is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
- and
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75. The method of claim 74, wherein the metal is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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76. The method of claim 74, wherein the metal is present in an amount at most about 0.2 wt % of the purified single-wall carbon nanotube material.
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77. A method for purifying carbon nanotubes comprising the steps of:
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(a) oxidizing a carbon nanotube material comprising carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere at a temperature between about 200°
C. and about 500°
C.;
(b) reoxidizing the carbon nanotube material at a temperature higher than the oxidizing step; and
(c) treating the carbon nanotube material with an aqueous solution comprising HCl.
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78. A method for purifying single-wall carbon nanotubes comprising the steps of:
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(a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere comprising carbon dioxide, wherein the carbon dioxide is at a concentration in the range of about 1 vol % and about 100 vol %; and
(b) treating the single-wall carbon nanotube material with a solution comprising a halogen-containing acid. - View Dependent Claims (79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120)
(a) performing a second oxidizing of the single-wall carbon nanotube material after the treating step, wherein the second oxidizing step is performed utilizing a gaseous atmosphere selected from the group consisting of the oxidizing gaseous atmosphere and a different oxidizing gaseous atmosphere than the oxidizing gaseous atmosphere; and
(b) performing a second treating of the single-wall carbon nanotube material after the second oxidizing step, wherein the second treating step is performed utilizing an acid solution selected from the group consisting of the solution comprising the halogen-containing acid, a first different solution comprising the halogen-containing acid, and a second different solution comprising a different halogen-containing acid.
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100. The method of claim 99 wherein the second oxidizing step is performed at the same temperature as the oxidizing step.
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101. The method of claim 99 wherein the second oxidizing step is performed at a temperature higher than the oxidizing step.
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102. The method of claim 78 further comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material.
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103. The method of claim 102, wherein the amorphous carbon is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
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104. The method of claim 103, wherein the amorphous carbon is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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105. The method of claim 102, wherein the amorphous carbon is present in an amount at most about 0.2 wt % of the purified single-wall carbon nanotube material.
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106. The method of claim 102 wherein
(a) the metallic impurity comprises metal; - and
(b) the metal is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
- and
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107. The method of claim 106, wherein the metal is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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108. The method of claim 106, wherein the metal is present in an amount at most about 0.1 wt % of the purified single-wall carbon nanotube material.
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109. The method of claim 102, wherein the recovering step comprises filtration.
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110. The method of claim 102, wherein the recovering step comprises washing the single-wall carbon nanotube material with water.
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111. The method of claim 102, wherein the recovering step comprises washing the single-wall carbon nanotube material with methanol.
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112. The method of claim 102, wherein the recovering step comprises drying the single-wall carbon nanotube material.
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113. The method of claim 112, wherein the drying step is performed in a vacuum.
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114. The method of claim 78 further comprising annealing the single-wall carbon nanotube material.
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115. The method of claim 114, wherein:
-
(a) the annealing step is performed at a temperature between about 600°
C. and about 1000°
C.; and
(b) the annealing step utilizes an annealing gas mixture comprising a gas selected from the group consisting of inert gases, nitrogen, carbon dioxide, and combinations thereof.
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116. The method of claim 115, wherein the annealing gas mixture further comprises water vapor.
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117. The method of claim 114, wherein the annealing step is performed in a vacuum.
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118. The method of claim 78 further comprising reduction of the single-wall carbon nanotube material.
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119. The method of claim 118, wherein the reduction step is performed at a temperature between about 250°
- C. and about 500°
C.
- C. and about 500°
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120. The method of claim 118, wherein the reduction step is performed with a gas comprising hydrogen gas.
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121. A method for purifying single-wall carbon nanotubes comprising the steps of:
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(a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere;
(b) treating the single-wall carbon nanotube material with a solution comprising a halogen-containing acid; and
(c) annealing the single-wall carbon nanotube material at a temperature between about 600°
C. and about 1000°
C.- View Dependent Claims (122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161)
(a) performing a second oxidizing of the single-wall carbon nanotube material after the treating step, wherein the second oxidizing step is performed utilizing a gaseous atmosphere selected from the group consisting of the oxidizing gaseous atmosphere and a different oxidizing gaseous atmosphere than the oxidizing gaseous atmosphere; and
(b) performing a second treating of the single-wall carbon nanotube material after the second oxidizing step, wherein the second treating step is performed utilizing an acid solution selected from the group consisting of the solution comprising the halogen-containing acid, a first different solution comprising the halogen-containing acid, and a second different solution comprising a different halogen-containing acid.
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143. The method of claim 142, wherein the second oxidizing step is performed at the same temperature as the oxidizing step.
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144. The method of claim 142 wherein the second oxidizing step is performed at a temperature higher than the oxidizing step.
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145. The method of claim 121 comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material.
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146. The method of claim 145, wherein the amorphous carbon is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
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147. The method of claim 145, wherein the amorphous carbon is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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148. The method of claim 145, wherein the amorphous carbon is present in an amount at most about 0.2 wt % of the purified single-wall carbon nanotube material.
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149. The method of claim 145, wherein
(a) the metallic impurity comprises metal; - and
(b) the metal is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.
- and
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150. The method of claim 149, wherein the metal is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.
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151. The method of claim 149, wherein the metal is present in an amount at most about 0.1 wt % of the purified single-wall carbon nanotube material.
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152. The method of claim 145, wherein the recovering step comprises filtration.
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153. The method of claim 145, wherein the recovering step comprises washing the single-wall carbon nanotube material with water.
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154. The method of claim 145, wherein the recovering step comprises washing the single-wall carbon nanotube material with methanol.
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155. The method of claim 145, wherein the recovering step comprises drying the single-wall carbon nanotube material.
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156. The method of claim 155, wherein the drying step is performed in a vacuum.
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157. The method of claim 121, wherein the annealing step utilizes an annealing gas mixture comprising water vapor.
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158. The method of claim 121, wherein the annealing step is performed in a vacuum.
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159. The method of claim 121, wherein further comprising reduction of the single-wall carbon nanotube material.
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160. The method of claim 159, wherein the reduction step is performed at a temperature between about 250°
- C. and about 500°
C.
- C. and about 500°
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161. The method of claim 159, wherein the reduction step is performed with a gas comprising hydrogen gas.
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Current AssigneeWilliam March Rice University
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Original AssigneeRice University
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InventorsHauge, Robert H., Chiang, Wan-Ting, Smalley, Richard E.
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Primary Examiner(s)Hendrickson, Stuart L.
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Assistant Examiner(s)Lish, Peter J
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Application NumberUS10/068,907Publication NumberTime in Patent Office865 DaysField of Search423/447.1, 423/447.2, 423/460, 423/445.RUS Class Current423/447.1CPC Class CodesB82Y 30/00 Nanotechnology for material...B82Y 40/00 Manufacture or treatment of...C01B 2202/02 Single-walled nanotubesC01B 32/17 PurificationD01F 11/121 Halogen, halogenic acids or...D01F 9/1278 Carbon monoxideY10S 977/75 Single-walledY10S 977/845 Purification or separation ...
