Growth Of Single-walled Carbon Nanotubes Research Articles

Study of field distribution characteristics in CVD reactors and enhanced growth of SWNCT

The low efficiency of growing single-walled carbon nanotubes (SWCNT) poses a barrier to their application in high-performance electronic devices. However, it is difficult to control the uniform growth of SWCNT in a floating catalytic reactor due to the complex parameter control. Therefore, it is essential to enhance the growth of SWCNT in the floating catalyst chemical vapor deposition (FCCVD) process. In the present work, the influence of the reactive flow field on the growth of SWCNT, which is often neglected, is revealed. To address this issue, this work combines experiments and simulations to obtain the characteristics of field distribution within the reactor and the trend of the products. The results of the flow field analysis indicate that thermal buoyancy is the cause of SWCNT growth limitation in FCCVD. By weakening the thermal buoyancy, a homogeneous reaction field is obtained; vortices in the flow field are reduced or even disappear; the temperature field is more homogeneous, and, importantly, the crystallinity of SWCNT is enhanced (IG/ID up to 20-fold). In addition, the decomposition process of the carbon source is also enhanced, thus suppressing the generation of by-products. Based on the results of the small tube experiments, both the increase in temperature and the decrease in residence time increased IG/ID. Furthermore, the distributions of the maximum and minimum diameters in SWCNT imply variations in the growth modes of SWCNT at different temperatures.

Towards the preparation of single-walled carbon nanotubes with average diameter of 1.2 nm

Preparation of single-walled carbon nanotubes (SWNTs) with diameters ranging from 1.2 to 1.5 nm has been highly demanded for field-effect transistors with superior properties. In the work, we report the chemical vapor deposition synthesis of SWNTs with an average diameter of 1.2 nm from a rationally designed nickel catalyst supported by magnesia. The high metal dispersion, the suitable reaction temperature, and the use of a methane carbon source co-determine the SWNT diameter distribution. Furthermore, through the synergistic application of poly(9,9-dioctylfluorene-2,7-diylalt-pyridine-2,6-diyl) wrapping and ultracentrifugation, SWNTs with enriched (10,8) species of 1.24 nm are successfully extracted, which is attributed to the selective interaction between the polymer molecules and the targeted SWNTs. This work not only sheds light on the growth of SWNTs with relatively large diameter, but also paves the way towards the preparation of high purity (n,m) species that could meet the requirements of advanced high-tech applications.

Single-walled carbon nanotube synthesis with RuRhPdIrPt high entropy alloy catalysts

Using high-entropy alloy nanoparticles (HEA NPs) composed of five platinum-group metals (5PGM), Ru, Rh, Pd, Ir, and Pt, as catalysts, we succeeded in growing single-walled carbon nanotubes (SWCNTs) via chemical vapor deposition (CVD). After CVD growth with C2H2 feedstock at 750 ℃ for 10 min, high-density SWCNTs were grown from 5PGM HEA NPs. The diameters of most SWCNTs were in the range of 0.83–1.1 nm, exhibiting the growth of small-diameter SWCNTs. Compared with monometal PGM catalysts, the SWCNT yield with the 5PGM HEA NP catalysts was much higher and was compatible even with those with Fe and Co.

Evolution Mechanism of Solid-Phase Catalysts During Catalytic Growth of Single-Walled Carbon Nanotubes.

Using solid nanoparticles (NPs) as catalysts is the most effective method to achieve catalytic growth of single-walled carbon nanotubes (SWCNTs) with ultrapure chirality. Until now, SWCNTs with a suitable chirality purity have not been prepared in experiments. That is, the evolution of solid NPs during the catalytic growth of SWCNTs is in contradiction with the original concept of a changeless structure. Hence, in this work, the evolution mechanism of solid cobalt NPs during the nucleation process of SWCNTs is analyzed through molecular dynamics. Similar to the experimental observations, the results show that a drastic structural fluctuation of the NPs occurs during the nucleation of SWCNTs. This structural fluctuation is caused by the fact that the elastic strain energy and surface energy of the NPs can be tuned when a carbon gradient exists between the subsurface and interior of the NP. Furthermore, such a carbon gradient can be reduced by changing the carbon feeding rate. This work not only reveals the evolution mechanism of solid catalysts during the nucleation of SWCNTs but also provides prospects for realizing solid catalysts with a changeless structure by tuning the experimental parameters.

Growth of Single-Walled Carbon Nanotubes from Solid Supported Heterogeneous Catalysts: Achievements and Challenges

Single-walled carbon nanotubes (SWNTs) have gained worldwide attention because of their exceptional electronic, optical, and mechanical properties, which are contingent on their structures denoted by chiral indices (n, m). To fully harness the extraordinary properties and advance SWNT-based technology, large scale synthesis of SWNTs with a narrow chirality distribution or even a specific (n, m) is highly demanded. Among various SWNT preparation techniques, chemical vapor deposition growth from solid supported heterogeneous catalysts has emerged as a promising approach in terms of large yield and (n, m) structure control. In this review, we provide an overview of the progress in developing heterogeneous catalysts for bulk synthesis of SWNTs. Firstly, the advantages and disadvantages of using solid supported catalysts for chemical vapor deposition growth of SWNTs are discussed. Secondly, the key components in supported catalysts, including the metallic component and the nature of support material, as well as their respective roles in affecting the catalyst performances and SWNT chirality distribution, are highlighted. Finally, the current challenges and future directions in the field of SWNT synthesis from solid supported catalysts are proposed.

Continuous gas-phase synthesis of iron nanoparticles at ambient conditions with controllable size and polydispersity

HypothesisBy altering aerosol growth dynamics with unipolar charges, one can obtain aerosols with narrow particles size distributions, a highly desirable feature in applications of functional nanoparticles. ExperimentsUnlike liquid colloid systems, aerosol particles in the free molecular regime undergo coarsening due to Brownian coagulation and will eventually attain a self-preserving size distribution with a typical geometric standard deviation of 1.46 - 1.48. We developed a novel continuous one-step aerosol synthesis reactor that produces iron nanoparticles from ferrocene at ambient conditions, which confines the site of precursor breakdown and particle formation in the downstream vicinity of a positive corona discharge. FindingsWe demonstrated that the particle size could be controlled within 3 - 10 nm with a suppressed geometric standard deviation (1.15 - 1.35). The as-produced iron nanoparticles were successfully used as catalyst for the growth of single-walled carbon nanotubes with a narrow diameter range. With a transient aerosol dynamics model, we showed that a fraction (as small as 0.1%) of unipolar-charged particles could have a significant impact on the aerosol growth dynamics, which eventually results in a narrower particle size distribution with smaller size and higher number concentrations.

Breaking the Axis-Symmetry of a Single-Wall Carbon Nanotube During Its Growth.

The asymmetrical growth of a single-wall carbon nanotube (SWCNT) by introducing a change of a local atomic structure, is usually inevitable and supposed to have a profound effect on the chirality control and property tailor. However, the breaking of the symmetry during SWCNT growth remains unexplored and its origins at the atomic-scale are elusive. Here, environmental transmission electron microscopy is used to capture the process of breaking the symmetry of a growing SWCNT from a sub-2-nm platinum catalyst nanoparticle in real-time, demonstrating that topological defects formed on the side of a SWCNT can serve as a buffer for stress release and inherently break its axis-symmetrical growth. Atomic-level details reveal the importance of the tube-catalyst interface and how the atom rearrangement of the solid-state platinum catalyst around the interface influences the final tubular structure. The active sites responsible for trapping carbon dimers and providing enough driving force for carbon incorporation and asymmetric growth are shown to be low-coordination step edges, as confirmed by theoretical simulations.

Chirality-selective growth of single-walled carbon nanotubes from layered double hydroxide supported monometallic catalysts

Chirality-selective growth of single-walled carbon nanotubes from layered double hydroxide supported monometallic catalysts

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.

Enhancement of ultimate tensile strength and ductility of copper matrix composites using a low content of single-wall carbon nanotubes

Single-wall carbon nanotube (SWCNT) reinforced copper (Cu) matrix composites were fabricated by a simple procedure of rotating mixing and then spark plasma sintering (SPS). It was found that addition of SWCNTs as low as 0.05 wt% can increase the ultimate tensile strength (223.5 MPa) and elongation rate (48.0%) of composites by 20.8% and 57.9%, respectively, relative to those (185 MPa and 30.4%) of pure Cu material, while the composite electrical conductivity retained a high value of 94.3% International Annealed Copper Standard (IACS). Mechanism analyses revealed that there are nanometer Ni particles tightly attached to SWCNTs, which were formed in situ during SWCNT growth by arc discharge method. These nanometer Ni particles promoted the bonding between SWCNTs and Cu matrix, leading to a fracture-mode change from intergranular in pure Cu material to ductile in the composites. The related factors to influence the microstructure of composites were discussed as well.

Highly selective growth of (6,5) single-walled carbon nanotubes from sigma phase alloy catalyst

Highly selective growth of (6,5) single-walled carbon nanotubes from sigma phase alloy catalyst

Modelling of the Flame Synthesis of Single-walled Carbon Nanotubes in Non-premixed Flames with Aerosol Catalyst

The use of aerosol catalyst in the flame synthesis of carbon nanotube (CNT) is known to yield single-walled CNT (SWCNT) that is useful for various applications. Modelling works are needed to optimize operating conditions for SWCNT growth but are unavailable. Therefore, a baseline model for the aerosol-catalyst system in flames is developed and the effect of oxygen on SWCNT growth is investigated. A baseline flame model for a normal diffusion flame with 24% oxygen concentration at the inlet is established via Computational Fluid Dynamic simulation. A dispersed phase model (DPM) is employed to simulate the entrainment of catalyst particles. The flame model is coupled with a published CNT growth rate model to predict the CNT growth rate at each particle. Inlet oxygen concentration is varied from 19% to 27% to study the effect of oxygen on SWCNT growth. Satisfactory validation of the baseline flame shape and temperature is established. Results show that particle 3 for the baseline case yields the highest CNT length compared to other particles due to the suitable path for the synthesis. The particles are classified based on the shortest time residence, moderate and longest time residence. Increasing oxygen concentration from 19% to 27% results in a 30% decrease in CNT length for particle 3 for each inlet condition due to lower carbon precursor and composition in the flame. Furthermore, the results showed that regardless of burner operating conditions, high SWCNT growth is consistently predicted between 120-140 mm HAB, which indicates the existence of an optimum range of species concentration for SWCNT growth in aerosol-based flame synthesis. Thus, it can be inferred that SWCNT growth in the aerosol–based method is highly dependent on carbon source and moderately dependent on temperature

The evolution mechanism of Mo catalyst at the initial stage of catalytic growth of single-walled carbon nanotubes

Molybdenum (Mo) nanoparticles (NPs) are one of the most effective refractory catalysts for preparing single-walled carbon nanotubes (SWCNTs) with high chirality. In this work, the evolution of Mo NPs at the initial stage of catalytic growth of SWCNT was investigated. It was found that NPs underwent transformation between the solid and semi-liquid phases during gradual deposition of C atoms, even though the deposition temperature was far below the melting point of NPs. Such transformation was caused by the elastic strain in NPs that could be manipulated by carbon (C) atoms. Furthermore, the results indicated that the lifetime of NPs in the semi-liquid state could be controlled by adjusting the feeding rate of C atoms. This work not only provides useful insight into the evolution of Mo NPs during the early stage of the catalytic growth of SWCNTs, but also opens up new prospects for controlling the lifetime of NPs in the semi-liquid phase by changing the experimental parameters.

Statistical patterns in high-throughput growth of single-wall carbon nanotubes from Co/Pt/Mo ternary catalysts

Designed alloy catalysts have shown promise in structure-controlled growth of single-wall carbon nanotubes (SWCNTs). However, due to the high-dimensional growth parameter space and low efficiency of the conventional trial-and-error optimizing approach, it is still challenging to explore and to establish the relations between catalyst compositions and the structure of SWCNTs. Here, we present a high-throughput strategy to investigate the statistical patterns in catalyst activity and selective growth of SWCNTs using Co/Pt/Mo ternary catalysts. Statistical analysis reveals that in the Co/Pt/Mo ternary diagram, there is an active region in the Co-rich Co–Mo corner to grow SWCNTs with high yield (≥25 tubes/μm2) and high quality (IG/ID ≥ 40). Enriched semiconducting (s-) SWCNTs with a purity higher than 90% were obtained along the boundary of the high yield region, near the Co–Pt axis. The statistical patterns of the yield, quality and selectivity are associated with the alloy composition, revealing a negative correlation between the yield and enrichment of s-SWCNTs. High-resolution transmission electron microscope characterization shows that a Co–Pt alloy catalyst with a uniform size distribution facilitates the s-SWCNT enrichment. And the separate phases of a Co–Mo/Co catalyst stabilize the active Co phase, leading to long catalyst lifetime and high yield of SWCNTs.

Role of Hydrogen in Ethylene-Based Synthesis of Single-Walled Carbon Nanotubes.

We examined the effect of hydrogen on the growth of single-walled carbon nanotubes in the aerosol (a specific case of the floating catalyst) chemical vapor deposition process using ethylene as a carbon source and ferrocene as a precursor for a Fe-based catalyst. With a comprehensive set of physical methods (UV-vis-NIR and Raman spectroscopies, transmission electron microscopy, scanning electron microscopy, differential mobility analysis, and four-probe sheet resistance measurements), we showed hydrogen to inhibit ethylene pyrolysis extending the window of synthesis parameters. Moreover, the detailed study at different temperatures allowed us to distinguish three different regimes for the hydrogen effect: pyrolysis suppression at low concentrations (I) followed by surface cleaning/activation promotion (II), and surface blockage/nanotube etching (III) at the highest concentrations. We believe that such a detailed study will help to reveal the complex role of hydrogen and contribute toward the synthesis of single-walled carbon nanotubes with detailed characteristics.

Growth of high-density single-wall carbon nanotubes with a uniform structure using a CoRu catalyst

The inefficient production of structurally uniform single-wall carbon nanotubes (SWCNTs) is an obstacle to their practical use in high-performance electronic devices. We have synthesized SWCNTs with a narrow diameter distribution (1.35 ± 0.25 nm) using a CoRu catalyst. Monodispersed nanoparticles with a narrow size distribution (2.4 ± 0.6 nm) and different compositions were prepared and used as catalysts for SWCNT growth. A furnace with an 80 cm-long uniform temperature zone (±10 °C) was designed and used to study the effect of catalyst composition on the growth of SWCNTs under the same conditions. By optimizing the composition of the bimetallic CoRu catalyst, SWCNTs with a uniform structure were efficiently synthesized. In addition, the effect of the growth conditions of temperature and carbon feed rate was investigated, and it was found that with an increase in yield, the structural uniformity of SWCNTs usually became worse. Both catalysts with elements in the suitable proportions and appropriate growth conditions are critical to achieving the high-efficiency structure-controlled growth of SWCNTs.

Bithiophene as a Sulfur-Based Promotor for the Synthesis of Carbon Nanotubes and Carbon-Carbon Composites.

We assess bithiophene (C8H6S2) as a novel sulfur-based promotor for the growth of single-walled carbon nanotubes (SWCNTs) in the aerosol (floating catalyst) CVD method. Technologically suitable equilibrium vapor pressure and an excess of hydrocarbon residuals formed under its decomposition make bithiophene an attractive promoter for the production of carbon nanotubes in general and specifically for ferrocene-based SWCNT growth. Indeed, we detect a moderate enhancement in the carbon nanotube yield and a decrease in the equivalent sheet resistance of the films at a low bithiophene content, indicating the improvement of the product properties. Moreover, the relatively high concentrations and low temperature stability of bithiophene result in non-catalytical decomposition, leading to the formation of pyrolytic carbon deposits; the deposits appear as few-layer graphene structures. Thus, bithiophene pyrolysis opens a route for the cheap production of hierarchical composite thin films comprising carbon nanotubes and few-layer graphene, which might be of practical use for hierarchical adsorbents, protective membranes, or electrocatalysis.

Single-walled carbon nanotube growth from Ni catalyst particles under conventional growth conditions by alcohol catalytic chemical vapor deposition: in situ X-ray absorption fine structure study

In situ X-ray absorption fine structure (XAFS) analysis was performed on Ni catalysts during the growth of single-walled carbon nanotubes (SWCNTs) by alcohol catalytic chemical vapor deposition (ACCVD). Ni catalysts were gradually reduced during the heating process and became metallic at the growth temperature (800 °C). With the addition of ethanol during SWCNT growth, Ni catalysts were slightly carbonized. Such behavior was similar to that observed for Ir catalysts in our previous study, although the Ni catalysts had a carbon composition of ∼5%. The results of this study demonstrated the growth of SWCNTs from almost metallic catalysts under the conventional growth conditions of ACCVD using Ni catalysts. Our result obtained by in situ XAFS analysis was consistent with the result of atomistic computer simulations.

(n, m) Distribution of Single-Walled Carbon Nanotubes Grown from a Non-Magnetic Palladium Catalyst

Non-magnetic metal nanoparticles have been previously applied for the growth of single-walled carbon nanotubes (SWNTs). However, the activation mechanisms of non-magnetic metal catalysts and chirality distribution of synthesized SWNTs remain unclear. In this work, the activation mechanisms of non-magnetic metal palladium (Pd) particles supported by the magnesia carrier and thermodynamic stabilities of nucleated SWNTs with different (n, m) are evaluated by theoretical simulations. The electronic metal-support interaction between Pd and magnesia upshifts the d-band center of Pd, which promotes the chemisorption and dissociation of carbon precursor molecules on the Pd surface, making the activation of magnesia-supported non-magnetic Pd catalysts for SWNT growth possible. To verify the theoretical results, a porous magnesia supported Pd catalyst is developed for the bulk synthesis of SWNTs by chemical vapor deposition. The chirality distribution of Pd-grown SWNTs is understood by operating both Pd-SWNT interfacial formation energy and SWNT growth kinetics. This work not only helps to gain new insights into the activation of catalysts for growing SWNTs, but also extends the use of non-magnetic metal catalysts for bulk synthesis of SWNTs.

Catalyst regeneration and multicycle growth of high purity and yield semiconducting single-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) with specific electrical types are urgently demanded for future nanoelectronic applications. However, it is still a challenge to simultaneously improve the purity and yield of semiconducting SWCNTs (s-SWCNTs). Herein, we propose a new multicycle approach to directly synthesize s-SWCNTs by chemical vapor deposition (CVD) using Fe0.01Mg0.99O as catalyst regeneration host. The appropriate carbon feedstock used in the first-time growth is CH4. During this process, the lattice oxygen would be released from Fe0.01Mg0.99O catalyst through H2 reduction and then form water vapor. The water vapor could in-situ selectively etch metallic SWCNTs (m-SWCNTs) in the nucleation process. After the termination of the first-time growth stage, the deactivative catalyst was regenerated by oxidation treatment, then it was reused to grow SWCNTs again. Carbon feedstock was changed to C2H5OH for the multicycle growth of SWCNTs and the secondary etching of as-grown m-SWCNTs and smaller-diameter SWCNTs. The selective synthesis of s-SWCNTs through this new multicycle growth process was up to 93.2% abundance, and the yield of SWCNTs was improved from 0.76% to 1.34% (weight ratio to the catalyst powder). It is interesting that there exists a diameter threshold value, which could affect the ∙OH groups etching on m-SWCNTs. According to the DFT simulation, the experimental results are related to the absorption capacity and reaction activity of SWCNTs. It presents a new approach to the massive synthesis of high purity s-SWCNTs and has wide applications in the future.