Carbon nanotubes have many material properties that make them attractive for applications. In the context of nanoelectronics, interest has focused on single-walled carbon nanotubes (SWNTs) because slight changes in tube diameter and wrapping angle, defined by the chirality indices (n, m), will shift their electrical conductivity from one characteristic of a metallic state to one characteristic of a semiconducting state, and will also change the bandgap. However, this structure-function relationship can be fully exploited only with structurally pure SWNTs. Solution-based separation methods yield tubes within a narrow structure range, but the ultimate goal of producing just one type of SWNT by controlling its structure during growth has proved to be a considerable challenge over the last two decades. Such efforts aim to optimize the composition or shape of the catalyst particles that are used in the chemical vapour deposition synthesis process to decompose the carbon feedstock and influence SWNT nucleation and growth. This approach resulted in the highest reported proportion, 55 per cent, of single-chirality SWNTs in an as-grown sample. Here we show that SWNTs of a single chirality, (12, 6), can be produced directly with an abundance higher than 92 per cent when using tungsten-based bimetallic alloy nanocrystals as catalysts. These, unlike other catalysts used so far, have such high melting points that they maintain their crystalline structure during the chemical vapour deposition process. This feature seems crucial because experiment and simulation both suggest that the highly selective growth of (12, 6) SWNTs is the result of a good structural match between the carbon atom arrangement around the nanotube circumference and the arrangement of the catalytically active atoms in one of the planes of the nanocrystal catalyst. We anticipate that using high-melting-point alloy nanocrystals with optimized structures as catalysts paves the way for total chirality control in SWNT growth and will thus promote the development of SWNT applications.
Single-walled carbon nanotubes (SWCNTs) have been attracting tremendous attention owing to their structure (chirality) dependent outstanding properties, which endow them with great potential in a wide range of applications. The preparation of chirality-pure SWCNTs is not only a great scientific challenge but also a crucial requirement for many high-end applications. As such, research activities in this area over the last two decades have been very extensive. In this review, we summarize recent achievements and accumulated knowledge thus far and discuss future developments and remaining challenges from three aspects: controlled growth, postsynthesis sorting, and characterization techniques. In the growth part, we focus on the mechanism of chirality-controlled growth and catalyst design. In the sorting part, we organize and analyze existing literature based on sorting targets rather than methods. Since chirality assignment and quantification is essential in the study of selective preparation, we also include in the last part a comprehensive description and discussion of characterization techniques for SWCNTs. It is our view that even though progress made in this area is impressive, more efforts are still needed to develop both methodologies for preparing ultrapure (e.g., >99.99%) SWCNTs in large quantity and nondestructive fast characterization techniques with high spatial resolution for various nanotube samples.
The growth of zigzag single-walled carbon nanotubes (SWNTs) is most challenging among all types of SWNTs, with the highest reported selectivity of ∼7%. Here we realized the dominant growth of (16,0) tubes at the abundance near ∼80% by using intermetallic W6Co7 catalysts containing plenty of (1 1 6) planes together with optimizing the growth conditions. These (1 1 6) planes may act as the structure templates for (16,0) SWNTs due to the geometrical match between the open end of the (16,0) tube and the atomic arrangements of the (1 1 6) planes in W6Co7. Using catalysts with designed structure as solid state template at suitable kinetic conditions offers a strategy for selective growth of zigzag SWNTs.
Semiconducting single-walled carbon nanotubes (s-SWNTs) with diameters of 1.0-1.5 nm (with similar bandgap to crystalline silicon) are highly desired for nanoelectronics. Up to date, the highest reported content of s-SWNTs as-grown is ∼97%, which is still far below the daunting requirements of high-end applications. Herein, we report a feasible and green pathway to use HO vapor to modulate the structure of the intermetallic WCo nanocrystals. By using the resultant WCo nanocatalysts with a high percentage of (1 0 10) planes as structural templates, we realized the direct growth of s-SWNT with the purity of ∼99%, in which ∼97% is (14,4) tubes (diameter 1.29 nm). HO can also act as an environmentally friendly and facile etchant for eliminating metallic SWNTs, and the content of s-SWNTs was further improved to 99.8% and (14,4) tubes to 98.6%. High purity s-SWNTs with even bandgap determined by their uniform structure can be used for the exquisite applications in different fields.
Compared with carbon nanotubes and graphene, graphene oxide (GO) exhibits excellent water solubility and biocompatibility in addition to the characteristic G band in Raman spectra. Therefore GO might be able to act as a flexible Raman probe to image cells or tissues through Raman mapping. However, the weak intensity of the G band restricts such applications of GO. Here we decorated GO with Au nanoparticles and found that the Raman intensity of GO in aqueous dispersions were remarkably enhanced by the surface enhancement effect. Therefore, rapid Raman imaging for Hela 229 cells was realized using Au/GO hybrids as Raman probes. The cell internalization mechanism of GO and Au/GO hybrids were also studied using Raman imaging. An endocytosis pathway was proposed from the results. In addition, the aqueous dispersions of Au/GO hybrids are stable for several weeks. Therefore, relying on the surface enhancement effect of Au nanoparticles, GO exhibits great potential as a general Raman imaging tool for biosystems.
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