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.

Enhancing the intrinsic activity and space time yield of Cu based heterogeneous methanol synthesis catalysts through CO2 hydrogenation is one of the major topics in CO2 conversion into value-added liquid fuels and chemicals. Here we report inverse ZrO2/Cu catalysts with a tunable Zr/Cu ratio have been prepared via an oxalate co-precipitation method, showing excellent performance for CO2 hydrogenation to methanol. Under optimal condition, the catalyst composed by 10% of ZrO2 supported over 90% of Cu exhibits the highest mass-specific methanol formation rate of 524 gMeOHkgcat−1h−1 at 220 °C, 3.3 times higher than the activity of traditional Cu/ZrO2 catalysts (159 gMeOHkgcat−1h−1). In situ XRD-PDF, XAFS and AP-XPS structural studies reveal that the inverse ZrO2/Cu catalysts are composed of islands of partially reduced 1–2 nm amorphous ZrO2 supported over metallic Cu particles. The ZrO2 islands are highly active for the CO2 activation. Meanwhile, an intermediate of formate adsorbed on the Cu at 1350 cm−1 is discovered by the in situ DRIFTS. This formate intermediate exhibits fast hydrogenation conversion to methoxy. The activation of CO2 and hydrogenation of all the surface oxygenate intermediates are significantly accelerated over the inverse ZrO2/Cu configuration, accounting for the excellent methanol formation activity observed.

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.