Chirality-selective Synthesis Research Articles

Supported catalysts derived from cobalt phyllosilicates for chemical vapor deposition growth of single-walled carbon nanotubes

Chemical vapor deposition (CVD) growth of single-walled carbon nanotubes (SWNTs) using supported catalyst is problematic due to possible metal coalescence during reaction. Thus, the development of supported catalyst that resists sintering is crucial for synthesizing SWNTs with a narrowly distributed chirality. Here, silica-supported phyllosilicate materials containing Co are prepared for catalytically growing carbon nanotubes. Owing to the incorporation of Co in the phyllosilicate, only part of Co2+ is reduced under CVD reaction environment, leading to the formation of immobilized metallic particles which subsequently catalyze the growth of SWNTs at 850 °C. With the addition of Pd promoter, the reducibility and carburization of the Co particles is enhanced, leading to the preferential synthesis of (6, 5) SWNTs at 600 °C. This work extends the application of phyllosilicates in catalytic synthesis of SWNTs, thus providing a new avenue for chirality-selective synthesis of SWNTs.

Synthesis, Sorting, and Applications of Single-Chirality Single-Walled Carbon Nanotubes.

The synthesis of high-quality chirality-pure single-walled carbon nanotubes (SWCNTs) is vital for their applications. It is of high importance to modernize the synthesis processes to decrease the synthesis temperature and improve the quality and yield of SWCNTs. This review is dedicated to the chirality-selective synthesis, sorting of SWCNTs, and applications of chirality-pure SWCNTs. The review begins with a description of growth mechanisms of carbon nanotubes. Then, we discuss the synthesis methods of semiconducting and metallic conductivity-type and single-chirality SWCNTs, such as the epitaxial growth method of SWCNT (“cloning”) using nanocarbon seeds, the growth method using nanocarbon segments obtained by organic synthesis, and the catalyst-mediated chemical vapor deposition synthesis. Then, we discuss the separation methods of SWCNTs by conductivity type, such as electrophoresis (dielectrophoresis), density gradient ultracentrifugation (DGC), low-speed DGC, ultrahigh DGC, chromatography, two-phase separation, selective solubilization, and selective reaction methods and techniques for single-chirality separation of SWCNTs, including density gradient centrifugation, two-phase separation, and chromatography methods. Finally, the applications of separated SWCNTs, such as field-effect transistors (FETs), sensors, light emitters and photodetectors, transparent electrodes, photovoltaics (solar cells), batteries, bioimaging, and other applications, are presented.

Subnanometer Single-Walled carbon nanotube growth from Fe-Containing Layered double hydroxides

High-quality single-walled carbon nanotubes (SWNTs) were synthesized on layered double hydroxides (LDHs) containing Fe and FeCo by CO chemical vapor deposition (CVD). Systematic investigations were performed to study the effects of temperature and catalyst composition on the diameter and chirality distributions of SWNTs. It was revealed that both catalysts produced subnanometer SWNTs at low reaction temperatures, correlated with the catalyst performances and reaction parameters. Particularly, SWNTs with enriched (6, 5) species were synthesized at 600 °C from LDHs containing bimetallic FeCo. Besides, the SWNT chirality distribution was further narrowed by a two-phase extraction method and the extracted (6, 5) SWNTs occupy about 57% of all semiconducting species. This work extends the development of robust LDH-based catalysts for chirality-selective synthesis of SWNTs, which paves the way to large scale production of subnanometer SWNTs for potential applications in electronics and optoelectronics.

Spontaneous gyrotropic electronic order in a transition-metal dichalcogenide.

Chirality is ubiquitous in nature, and populations of opposite chiralities are surprisingly asymmetric at fundamental levels1,2. Examples range from parity violation in the subatomic weak force to homochirality in biomolecules. The ability to achieve chirality-selective synthesis (chiral induction) is of great importance in stereochemistry, molecular biology and pharmacology2. In condensed matter physics, a crystalline electronic system is geometrically chiral when it lacks mirror planes, space-inversion centres or rotoinversion axes1. Typically, geometrical chirality is predefined by the chiral lattice structure of a material, which is fixed on formation of the crystal. By contrast, in materials with gyrotropic order3-6, electrons spontaneously organize themselves to exhibit macroscopic chirality in an originally achiral lattice. Although such order-which has been proposed as the quantum analogue of cholesteric liquid crystals-has attracted considerable interest3-15, no clear observation or manipulation of gyrotropic order has been achieved so far. Here we report the realization of optical chiral induction and the observation of a gyrotropically ordered phase in the transition-metal dichalcogenide semimetal 1T-TiSe2. We show that shining mid-infrared circularly polarized light on 1T-TiSe2 while cooling it below the critical temperature leads to the preferential formation of one chiral domain. The chirality of this state is confirmed by the measurement of an out-of-plane circular photogalvanic current, the direction of which depends on the optical induction. Although the role of domain walls requires further investigation with local probes, the methodology demonstrated here can be applied to realize and control chiral electronic phases in other quantum materials4,16.

Iron silicide-catalyzed growth of single-walled carbon nanotubes with a narrow diameter distribution

Single-walled carbon nanotubes (SWNTs) are synthesized from iron silicide (FeSi) catalyst by the chemical vapor deposition (CVD). During the growth process, Fe atoms migrate onto the FeSi surface and form active Fe nanoparticles, catalyzing the growth of SWNTs. The produced SWNTs demonstrate a narrow diameter/chirality distribution, possibly arising from the solid state of Fe nanoparticles and the use of carbon monoxide (CO) as the carbon source, which facilitates SWNT growth by perpendicular mode. Remarkably, (12, 6) SWNTs occupies more than 40% of all the SWNTs, as detected by Raman spectroscopy. This work opens an avenue for chirality selective synthesis of SWNTs by applying silicide as the catalyst.

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.

Preferential synthesis of (6,4) single-walled carbon nanotubes by controlling oxidation degree of Co catalyst

Chirality-selective synthesis of single-walled carbon nanotubes (SWNTs) has been a research goal for the last two decades and is still challenging due to the difficulty in controlling the atomic structure in the one-dimensional material. Here, we develop an optimized approach for controlling the chirality of species by tuning the oxidation degree of Co catalyst. Predominant synthesis of (6,4) SWNTs is realized for the first time. The detailed mechanism is investigated through a systematic experimental study combined with first-principles calculations, revealing that the independent control of tube diameter and chiral angle achieved by changing the binding energy between SWNTs (cap and tube edge) and catalyst causes a drastic transition of chirality of SWNTs from (6,5) to (6,4). Since our approach of independently controlling the diameter and chiral angle can be applied to other chirality species, our results can be useful in achieving the on-demand synthesis of specific-chirality SWNTs.

"Smart poisoning" of Co/SiO2 catalysts by sulfidation for chirality-selective synthesis of (9,8) single-walled carbon nanotubes.

The chirality-selective synthesis of relatively large (diameter > 1 nm) single-walled carbon nanotubes (SWCNTs) is of great interest for a variety of practical applications, but only a few catalysts are available so far. Previous studies suggested that S (compounds) can enhance the chirality-selectivity of Co catalysts in SWCNT synthesis, however, the mechanism behind is not fully understood, and no tailorable methodology has yet been developed. Here, we demonstrate a facile approach to achieve the chirality-selective synthesis of SWCNTs by the sulfidation-based poisoning of silica-supported Co catalysts using a mixture of H2S and H2. The UV-vis-NIR, photoluminescence, and Raman spectroscopy results together show that the resulting SWCNTs have a narrow diameter distribution of around 1.2 nm, and (9,8) nanotubes have an abundance of ∼38% among the semiconducting species. More importantly, the carbon yield achieved by the sulfided catalyst (2.5 wt%) is similar to that of the nonsulfided one (2.7 wt%). The characterization of the catalysts by X-ray diffraction, X-ray photoelectron spectroscopy, X-ray fluorescence, and H2 temperature-programmed reduction shows that the sulfidation leads to the formation of Co9S8 nanoparticles. However, Co9S8 nanoparticles are reduced back to regenerate metallic Co nanoparticles during the synthesis of SWCNTs, which maintain a high carbon yield. In this process, Co9S8 nanoparticles seemingly intermediate the production of Co nanoparticles with narrow size distribution. Due to the fact that the poisoning step improves the quality of the end-product rather than hampering the growth process, we have coined the process developed as "smart poisoning". This study not only reveals the mechanism behind the beneficial role of S in the selective synthesis of relatively large SWCNTs but also presents a promising method to create chirality-selective catalysts with high activity for scalable synthesis.

Chirality-selective synthesis of carbon nanotubes by catalytic-chemical vapor deposition using quasicrystal alloys as catalysts

Abstract We study ultrathin quasicrystalline (QC) films as catalysts for the synthesis of carbon nanotubes (CNTs). To optimize the conditions for the synthesis of CNTs with single chirality, it is important to understand the effects of the catalyst on the chirality-selectivity. Among QC alloys found so far, an icosahedral Al–Cu–Fe alloy system with fivefold symmetry was tested for a catalyst in the synthesis of CNTs by alcohol catalytic-chemical vapor deposition (CCVD). Cross-sectional scanning electron microscopic images of the samples revealed that vertically-aligned CNTs were synthesized reproducibly. It implies that QC films have a significant catalytic activity for the synthesis of CNTs. Moreover, preliminary results of chirality-selectivity are obtained by means of resonance Raman scattering. It is suggested that Al–Cu–Fe ultrathin films are useful for the preferential synthesis of armchair-type CNTs, that is, QC nanoclusters play an important role as catalyst in alcohol CCVD.