Maoshuai He

Chiral-Selective Growth of Single-Walled Carbon Nanotubes on Lattice-Mismatched Epitaxial Cobalt Nanoparticles

Controlling chirality in growth of single-walled carbon nanotubes (SWNTs) is important for exploiting their practical applications. For long it has been conceptually conceived that the structural control of SWNTs is potentially achievable by fabricating nanoparticle catalysts with proper structures on crystalline substrates via epitaxial growth techniques. Here, we have accomplished epitaxial formation of monometallic Co nanoparticles with well-defined crystal structure, and its use as a catalyst in the selective growth of SWNTs. Dynamics of Co nanoparticles formation and SWNT growth inside an atomic-resolution environmental transmission electron microscope at a low CO pressure was recorded. We achieved highly preferential growth of semiconducting SWNTs (~90%) with an exceptionally large population of (6, 5) tubes (53%) in an ambient CO atmosphere. Particularly, we also demonstrated high enrichment in (7, 6) and (9, 4) at a low growth temperature. These findings open new perspectives both for structural control of SWNTs and for elucidating the growth mechanisms.

Predominant (6,5) Single-Walled Carbon Nanotube Growth on a Copper-Promoted Iron Catalyst

We have developed a magnesia (MgO)-supported iron-copper (FeCu) catalyst to accomplish the growth of single-walled carbon nanotubes (SWNTs) using carbon monoxide (CO) as the carbon source at ambient pressure. The FeCu catalyst system facilitates the growth of small-diameter SWNTs with a narrow diameter distribution. UV-vis-NIR optical absorption spectra and photoluminescence excitation (PLE) mapping were used to evaluate the relative quantities of the different (n,m) species. We have also demonstrated that the addition of Cu to the Fe catalyst can also cause a remarkable increase in the yield of SWNTs. Finally, a growth mechanism for the FeCu-catalyzed synthesis of SWNTs has been proposed.

Diameter and chiral angle distribution dependencies on the carbon precursors in surface-grown single-walled carbon nanotubes

Carbon nanotubes grown from discrete Fe-containing nanoparticles dispersed on a silicon nitride transmission electron microscope grid were systematically studied. The (n,m) indices of produced single-walled carbon nanotubes (SWNTs) were deduced from their electron diffraction patterns. Relatively small diameter SWNTs with a narrow diameter distribution (0.7-1.6 nm) were produced using CO as the carbon source at 800 °C, while large diameter SWNTs ranging from 1.0 nm to 4.7 nm were synthesized when using CH(4) as the carbon source. The chiral angle distributions of the SWNTs produced from different carbon sources are also different, which are attributed to the preferred cap nucleation associated with the carbon feed rate on the catalyst instead of carbon nanotube growth kinetics. Furthermore, growth of carbon laminar nanoclusters inside carbon nanotubes was achieved at a higher growth temperature, suggesting that dissociated carbon diffuses across the nanoparticle during the nanotube growth process.

Precise Determination of the Threshold Diameter for a Single-Walled Carbon Nanotube To Collapse

Closed-edged bilayer graphene nanoribbons were formed by the spontaneous collapse of large-diameter single-walled carbon nanotubes (SWNTs) grown on gold nanoparticles by chemical vapor deposition. Such bilayer graphene nanoribbons could adopt different stacking configurations, such as AB-stacking or stacking order with any rotation angle, correlated with the chiral angles of their parent rounded SWNTs. On the basis of the electron diffraction characterizations on a good number of collapsed and uncollapsed SWNTs, the threshold diameter for SWNTs to collapse was precisely determined to be 5.1 nm, independent of the chiral angle of the SWNTs. The determination is consistent with that calculated by both classical adaptive intermolecular reactive empirical bond order force field and density functional theory after having taken the stacking effect and thermal fluctuation into account.

Single-walled carbon nanotube networks for ethanol vapor sensing applications

AbstractNetworks of pristine high quality single walled carbon nanotubes (SWNTs), the SWNTs after Ar-plasma treatment (from 2 to 12 min) and carbon nanobuds (CNBs) have been tested for ethanol vapor sensing. It was found that the pristine high quality SWNTs do not exhibit any ethanol sensitivity, while the introduction of defects in the tubes results in the appearance of the ethanol sensitivity. The CNB network showed ethanol sensitivity without plasma treatment. Both CNB and low defect (after 3 min treatment) SWNT networks exhibit significant drift in the resistance baseline, while heavily plasma-treated (9 min) SWNTs exhibited high ethanol vapor sensitivity without the baseline change. The mechanisms of the ethanol sensitivity and stability after the plasma irradiation are attributed to the formation of sensitive dangling bonds in the SWNTs and formation of defect channels facilitating access of the ethanol vapor to all parts of the bundled nanotubes.

Insights into chirality distributions of single-walled carbon nanotubes grown on different CoxMg1−xO solid solutions

Low-temperature chemical vapor deposition (CVD) growth of single-walled carbon nanotubes (SWNTs) was achieved on two different types of CoxMg1−xO catalysts prepared by different techniques: atomic layer deposition (ALD) and impregnation. The chirality distribution of SWNTs grown on the ALD-prepared CoxMg1−xO catalyst is wider than that of SWNTs grown on the impregnation-prepared CoxMg1−xO catalyst. The different chirality distributions of SWNTs are related to their different growth modes. The ALD-prepared CoxMg1−xO catalyzes the growth of SWNTs by “tip growth” mode, as revealed by in situ environmental transmission electron microscopy studies. In contrast, SWNTs grow on the impregnation-prepared CoxMg1−xO by “base growth” mode. “Base growth” is attributed to strong metal–support interactions between the epitaxially formed Co nanoparticles and the underlying MgO support, accounting for the synthesis of SWNTs with high chiral-selectivity. In addition, impregnation-prepared CoxMg1−xO catalysts calcinated at different temperatures were systematically studied and their catalytic performances in synthesizing carbon nanotubes were elucidated. This work illustrates the influence of metal–support interactions and catalyst reducibility on the chirality-distribution of the synthesized SWNTs.

Growth of single-walled carbon nanotubes with large chiral angles on rhodium nanoparticles

Single-walled carbon nanotubes (SWNTs) grown on rhodium (Rh) nanoparticles were demonstrated to have large chiral angles and a preference for metallic tubes.

Growth Termination and Multiple Nucleation of Single-Wall Carbon Nanotubes Evidenced by in Situ Transmission Electron Microscopy

In order to controllably grow single-wall carbon nanotubes (SWCNTs), a better understanding of the growth processes and how they are influenced by external parameters such as catalyst and gaseous environment is required. Here, we present direct evidence of growth termination of individual SWCNTs and successive growth of additional SWCNTs on Co catalyst particles supported on MgO by means of environmental transmission electron microscopy. Such in situ observations reveal the plethora of solid carbon formations at the local scale while it is happening and thereby elucidate the multitude of configurations resulting from identical external synthesis conditions, which should be considered in the quest for controlled SWCNT growth. Using CO and a mixture of CO and H2 as carbon sources, we show that the growth of SWCNTs terminates with a reduced tube-catalyst adhesion strength. Two main reasons for the cessation are proposed: insufficient active carbon species and a certain amount of stress exerted at the tube-catalyst interface. Interestingly, it was observed that catalyst particles stayed active in terms of nucleating additional solid carbon structures after growth termination of the first SWCNT. These observations elucidate the importance of an in-depth understanding of the role of catalysts and carbon sources in the continued growth of SWCNTs. Furthermore, it serves as a guide for further control of carbon nanostructure synthesis via catalyst engineering and synthesis optimization.

Growth Modes and Chiral Selectivity of Single-Walled Carbon Nanotubes

Chemical vapor deposition synthesis of single-walled carbon nanotubes, using an Fe catalyst, and alternating methane and carbon monoxide as carbon feedstocks, leads to the reversible formation of junctions between tubes of different diameters. Combined with an atomistic modeling of the tube/catalyst interface, this shows that the ratio of diameters of the tube and its seeding particle, denoting the growth mode, depends on the carbon fraction inside the catalyst. With carbon monoxide, nanoparticles are strongly carbon enriched, and tend to dewet the tube, in a perpendicular growth mode. Cross-checking our results with the available reports from the literature of the last decade strongly suggests that these latter conditions should favor the near armchair chiral selectivity observed empirically.

Designing Catalysts for Chirality‐Selective Synthesis of Single‐Walled Carbon Nanotubes: Past Success and Future Opportunity

A major obstacle for the applications of single-walled carbon nanotubes (SWNTs) in electronic devices is their structural diversity, ending in SWNTs with diverse electrical properties. Catalytic chemical vapor deposition has shown great promise in directly synthesizing high-quality SWNTs with a high selectivity to specific chirality (n, m). During the growth process, the tube-catalyst interface plays crucial roles in regulating the SWNT nucleation thermodynamics and growth kinetics, ultimately governing the SWNT chirality distribution. Starting with the introduction of SWNT growth modes, this review seeks to extend the knowledge about chirality-selective synthesis by clarifying the energetically favored SWNT cap nucleation and the threshold step for SWNT growth, which describes how the tube-catalyst interface affects both the nucleus energy and the new carbon atom incorporation. Such understandings are subsequently applied to interpret the (n, m) specific growth achieved on a variety of templates, such as SWNT segments or predefined molecular seeds, transition metal (Fe, Co and Ni)-containing catalysts at low reaction temperatures, W-based alloy catalysts, and metal carbides at relatively high reaction temperatures. The up to date achievements on chirality-controlled synthesis of SWNTs is summarized and the remaining major challenges existing in the SWNT synthesis field are discussed.