Raman spectroscopy of iodine-doped double-walled carbon nanotubes

We present a Raman spectroscopy study of iodine-intercalated (p-type-doped) double-walled carbon nanotubes. Double-walled carbon nanotubes (DWCNTs) are synthesized by catalytic chemical vapor deposition and characterized by Raman spectroscopy. The assignment of the radial breathing modes and the tangential modes of pristine DWCNTs is done in the framework of the bond polarization theory, using the spectral moment method. The changes in the Raman spectrum upon iodine doping are analyzed. Poly-iodine anions are identi- fied, and the Raman spectra reveal that the charge transfer between iodine and DWCNTs only involves the outer tubes

An investigation of carbon nanotubes obtained from the decomposition of methane over reduced Mg1− xM xAl2O4 spinel catalysts

Carbon nanotubes produced by the treatment of Mg1−xMxAl2O4 (M = Fe, Co, or Ni; x = 0.1, 0.2, 0.3, or 0.4) spinels with an H2–CH4 mixture at 1070 °C have been investigated systematically. The grains of the oxide-metal composite particles are uniformly covered by a weblike network of carbon nanotube bundles, several tens of micrometers long, made up of single-wall nanotubes with a diameter close to 4 nm. Only the smallest metal particles (<5 nm) are involved in the formation of the nanotubes. A macroscopic characterization method involving surface area measurements and chemical analysis has been developed in order to compare the different nanotube specimens. An increase in the transition metal content of the catalyst yields more carbon nanotubes (up to a metal content of 10.0 wt% or x = 0.3), but causes a decrease in carbon quality. The best compromise is to use 6.7 wt% of metal (x = 0.2) in the catalyst. Co gives superior results with respect to both the quantity and quality of the nanotubes. In the case of Fe, the quality is notably hampered by the formation of Fe3C particles

Microhardness and friction coefficient of multi-walled carbon nanotube-yttria-stabilized ZrO2 composites prepared by spark plasma sintering

Multi-walled carbon nanotubes (eight walls) are mixed with an yttria-stabilized ZrO2 powder. The specimens are densified by spark plasma sintering. Compared to ZrO2, there is a 3.8-fold decrease of the friction coefficient against alumina upon the increase in carbon content. Examinations of the friction tracks show that wear is very low when the carbon content is sufficient. Exfoliation of the nanotubes due to shearing stresses and incorporation of the debris into a lubricating film over the contact area is probable

A Study of the Formation of Single- and Double-Walled Carbon Nanotubes by a CVD Method

The reduction in H2/CH4 atmosphere of aluminum-iron oxides produces metal particles small enough to catalyze the formation of single-walled carbon nanotubes. Several experiments have been made using the same temperature profile and changing only the maximum temperature (800-1070 °C). Characterizations of the catalyst materials are performed using notably 57Fe Mo¨ssbauer spectroscopy. Electron microscopy and a macroscopical method are used to characterize the nanotubes. The nature of the iron species (Fe3+, R-Fe, ç-Fe-C, Fe3C) is correlated to their location in the material. The nature of the particles responsible for the high-temperature formation of the nanotubes is probably an Fe-C alloy which is, however, found as Fe3C by postreaction analysis. Increasing the reduction temperature increases the reduction yield and thus favors the formation of surface-metal particles, thus producing more nanotubes. The obtained carbon nanotubes are mostly single-walled and double-walled with an average diameter close to 2.5 nm. Several formation mechanisms are thought to be active. In particular, it is shown that the second wall can grow inside the first one but that subsequent ones are formed outside. It is also possible that under given experimental conditions, the smallest (<2 nm) catalyst particles preferentially produce double-walled rather than single-walled carbon nanotubes

Carbon nanotubes grown in situ by a novel catalytic method

Carbon nanotubes can be produced by the catalytic decomposition of hydrocarbons on small metal particles. However, nanotubes are generally produced together with non-tubular filaments and tubes coated by pyrolytic carbon. We propose a novel catalyst method for the in situ production, in a composite powder, of a huge amount of single- and multiwalled carbon nanotubes, having a diameter between 1.5 and 15 nm and arranged in bundles up to 100 mm long. We anticipate that dense materials prepared from such composite powders could have interesting mechanical and physical properties

Carbon Nanotubes by a CVD Method. Part II: Formation of Nanotubes from (Mg, Fe)O Catalysts

The aim of this paper is to study the formation of carbon nanotubes (CNTs) from different Fe/MgO oxide powders that were prepared by combustion synthesis and characterized in detail in a companion paper. Depending on the synthesis conditions, several iron species are present in the starting oxides including Fe2+ ions, octahedral Fe3+ ions, Fe3+ clusters, and MgFe2O4-like nanoparticles. Upon reduction during heating at 5 °C/min up to 1000 °C in H2/CH4 of the oxide powders, the octahedral Fe3+ ions tend to form Fe2+ ions, which are not likely to be reduced to metallic iron whereas the MgFe2O4-like particles are directly reduced to metallic iron. The reduced phases are R-Fe, Fe3C, and ç-Fe-C. Fe3C appears as the postreaction phase involved in the formation of carbon filaments (CNTs and thick carbon nanofibers). Thick carbon nanofibers are formed from catalyst particles originating from poorly dispersed species (Fe3+ clusters and MgFe2O4-like particles). The nanofiber outer diameter is determined by the particle size. The reduction of the iron ions and clusters that are well dispersed in the MgO lattice leads to small catalytic particles (<5 nm), which tend to form SWNTS and DWNTs with an inner diameter close to 2 nm. Well-dispersed MgFe2O4-like particles can also be reduced to small metal particles with a narrow size distribution, producing SWNTs and DWNTs. The present results will help in tailoring oxide precursors for the controlled formation of CNTs

Carbon Nanotubes by a CVD Method. Part I: Synthesis and Characterization of the (Mg, Fe)O Catalysts

The controlled synthesis of carbon nanotubes by chemical vapor deposition requires tailored and wellcharacterized catalyst materials. We attempted to synthesize Mg1-xFexO oxide solid solutions by the combustion route, with the aim of performing a detailed investigation of the influence of the synthesis conditions (nitrate/urea ratio and the iron content) on the valency and distribution of the iron ions and phases. Notably, characterization of the catalyst materials is performed using 57Fe Mo¨ssbauer spectroscopy, X-ray diffraction, and electron microscopy. Several iron species are detected including Fe2+ ions substituting for Mg2+ in the MgO lattice, Fe3+ ions dispersed in the octahedral sites of MgO, different clusters of Fe3+ ions, and MgFe2O4-like nanoparticles. The dispersion of these species and the microstructure of the oxides are discussed. Powders markedly different from one another that may serve as model systems for further study are identified. The formation of carbon nanotubes upon reduction in a H2/CH4 gas atmosphere of the selected powders is reported in a companion paper

Mössbauer Spectroscopy Involved in the Study of the Catalytic Growth of Carbon Nanotubes

Single-walled and thin multiwalled carbon nanotubes are prepared by a catalytic-chemical-vapor-deposition method involving the simultaneous formation of Fe or Co nanometric particles from oxide solid solutions based on Al2O3, MgAl2O4 or MgO. This paper is an overview of the authors’ work on the characterization by Mössbauer spectroscopy used in complement to electron microscopy and specific-surface-area measurements. It is notably attempted to correlate the nature of the different iron phases in the carbon nanotube-metal-oxide powders with the formation mechanisms of the nanotubes. Massive composites and hydrogen storage are proposed as possible applications

Fe-substituted mullite powders for the in situ synthesis of carbon nanotubes by catalytic chemical vapor deposition

Powders of iron-substituted mullite were prepared by combustion and further calcination in air at different temperatures. A detailed study involving notably Mo¨ssbauer spectroscopy showed that the Fe3+ ions are distributed between the mullite phase and a corundum phase that progressively dissolves into mullite upon the increase in calcination temperature. Carbon nanotube-Fe-mullite nanocomposites were prepared for the first time by a direct method involving a reduction of these powders in H2-CH4 and without any mechanical mixing step. The carbon nanotubes formed by the catalytic decomposition of CH4 on the smallest metal particles are mostly double-walled and multiwalled, although some carbon nanofibers are also observed

Fe/Co Alloys for the Catalytic Chemical Vapor Deposition Synthesis of Single- and Double-Walled Carbon Nanotubes (CNTs). 1. The CNT−Fe/Co−MgO System

Mg0.90FexCoyO (x + y ) 0.1) solid solutions were synthesized by the ureic combustion route. Upon reduction at 1000 °C in H2-CH4 of these powders, Fe/Co alloy nanoparticles are formed, which are involved in the formation of carbon nanotubes, which are mostly single and double walled, with an average diameter close to 2.5 nm. Characterizations of the materials are performed using 57Fe Mo¨ssbauer spectroscopy and electron microscopy, and a well-established macroscopic method, based on specific-surface-area measurements, was applied to quantify the carbon quality and the nanotubes quantity. A detailed investigation of the Fe/Co alloys’ formation and composition is reported. An increasing fraction of Co2+ ions hinders the dissolution of iron in the MgO lattice and favors the formation of MgFe2O4-like particles in the oxide powders. Upon reduction, these particles form R-Fe/Co particles with a size and composition (close to Fe0.50Co0.50) adequate for the increased production of carbon nanotubes. However, larger particles are also produced resulting in the formation of undesirable carbon species. The highest CNT quantity and carbon quality are eventually obtained upon reduction of the iron-free Mg0.90Co0.10O solid solution, in the absence of clusters of metal ions in the starting material. Introduction Catalyti