Rai Pradeep K, Pinnick Robert A, Parra-Vasquez A Nicholas G, Davis Virginia A, Schmidt Howard K, Hauge Robert H, Smalley Richard E, Pasquali Matteo
Carbon Nanotechnology Laboratory, Center for Nanoscale Science and Technology, Rice University, Houston, Texas 77005, USA.
J Am Chem Soc. 2006 Jan 18;128(2):591-5. doi: 10.1021/ja055847f.
We present the first quantitative assessment of the maximum amount of nanotubes that can exist in the isotropic phase () of single-walled carbon nanotubes (SWNTs) in Brønsted-Lowry acids. We employ a centrifugation technique in conjunction with UV-vis-nIR spectroscopy to quantify , which is also the critical concentration of the isotropic-nematic transition of SWNTs in strong acids. Centrifugation of biphasic dispersions of SWNTs, that is, acid dispersions consisting of an isotropic phase in equilibrium with an ordered nematic liquid crystalline phase, results in a clear phase separation, where the isotropic phase is supernatant. Dilution of the isotropic phase with a known amount of acid followed by UV-vis-nIR absorbance measurements yields , that is, the maximum concentration of SWNTs that can exist in the isotropic phase in a given acid for a given SWNTs' length distribution. At low SWNT concentration (below 200 ppm) in superacids, light absorbance in the range from 400 to 1400 nm scales linearly with concentration. This Beer's law behavior yields calibration curves for measuring SWNTs' concentration in acids. We find that the critical concentration of the isotropic-nematic transition increases with acid strength in accordance with the previously proposed sidewall protonation mechanism for dispersing SWNTs in acids.
我们首次对布朗斯特-劳里酸中单壁碳纳米管(SWNTs)各向同性相()中能够存在的纳米管最大量进行了定量评估。我们采用离心技术结合紫外-可见-近红外光谱来量化,这也是强酸中SWNTs各向同性-向列相转变的临界浓度。对SWNTs的双相分散体(即由与有序向列型液晶相平衡的各向同性相组成的酸分散体)进行离心,会导致明显的相分离,其中各向同性相在上清液中。用已知量的酸稀释各向同性相,然后进行紫外-可见-近红外吸光度测量,可得出,即在给定的酸中,对于给定的SWNTs长度分布,能够存在于各向同性相中的SWNTs的最大浓度。在超强酸中SWNT浓度较低(低于200 ppm)时,400至1400 nm范围内的吸光度与浓度呈线性关系。这种符合比尔定律的行为产生了用于测量酸中SWNTs浓度的校准曲线。我们发现,根据先前提出的将SWNTs分散在酸中的侧壁质子化机制,各向同性-向列相转变的临界浓度随酸强度的增加而增加。