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Structural phase stability and homogeneity of the electrochemically synthesized Mn2V2O7 (MVO) on nanocarbon network structures are investigated. The cup-stacked multi-walled carbon nanotubes (CNTs) and electrolytic graphene oxide (eGO) are the networks exploited in present work. It is shown that co-electrodeposition of carbonaceous network and V2O5.nH2O followed by electro-insertion of Mn2+ cations results in the formation of intermixed β-Mn2V2O7 nano-structures. The morphology and surface chemistry of the synthesized nano-structures is studied via high-resolution electron transmission and scanning X-ray photo-emission microscopies as well as Raman spectroscopy. The synthesized MVO on carbon fiber surface in the absence of the nanocarbon network shows a non-uniform phase formation and uneven coating distribution. The nanocarbon networks assisted MVO demonstrate uniform phase formation and distribution. The dominant MVO structural phase product present in these samples differs with different type of carbonaceous networks. The possible effect of the catalytic activity of the carbonaceous network as well as their hydrophilicity on the final structural and phase formation is discussed. The present study establishes new possibilities on catalytic assisted metal alloy oxide deposition for advanced applications.

Raman spectroscopy and in situ Raman spectroelectrochemistry were applied to study the selective etching of thin tubes by lithium vapor in doped single-walled carbon nanotubes (SWCNTs). A strong doping of SWCNTs after the reaction with Li vapor was confirmed by the vanishing of the radial breathing mode (RBM) and by a strong attenuation of the tangential displacement (TG) band in the Raman spectra. The Raman spectra of the Li-vapor-treated SWCNTs after subsequent reaction with water showed changes in the diameter distribution compared with that of a pristine sample (nanotubes with diameters of <1 nm disappeared from the Raman spectra). The samples were tested by the Raman pattern with five different laser lines, and a removal of narrower tubes was confirmed. The remaining wider tubes were not significantly damaged by the treatment with Li, as indicated by the D line in the Raman spectra. Furthermore, the small-diameter tubes are converted not into amorphous carbon but into lithium carbide, which could easily be removed by hydrolysis. The treated samples were further charged electrochemically. It was shown by spectroelectrochemistry that anodic charging may lead to removal of the residual chemical doping from the thicker nanotubes in the sample, but the thin nanotubes did not appear in the spectra. This is a further confirmation of the removal of the small-diameter tubes.

Raman spectroscopy and in situ Raman spectroelectrochemistry have been applied to the study of the lithium vapor doping of C60@SWCNTs (peapods; SWCNT=single-walled carbon nanotube). A strong degree of doping was proven by the disappearance of the radial breathing mode (RBM) of the SWCNTs and by the attenuation of the tangential (TG) band intensity by two orders of magnitude. The lithium doping causes a downshift of the Ag(2) mode of the intratubular C60 by 27 cm(-1) and changes the resonance condition of the encapsulated fullerene. In contrast to potassium vapor doping, the strong downshift of the TG band was not observed for lithium doping. The peapods treated with lithium vapor remained partially doped even when they were exposed to humid air. This was reflected by a reduction in the intensity of the nanotube and the fullerene modes and by the change in the shape of the RBM band compared with that of the undoped sample. The Ag(2) mode of the intratubular fullerene was not resolved after contact of the lithium-doped sample with water. Lithium insertion into the interior of a peapod and its strong interaction with the intratubular fullerene is suggested to be responsible for the air-insensitive residual doping. This residual doping was confirmed by in situ spectroelectrochemical measurements. The TG band of the lithium-doped peapods did not undergo an upshift during the anodic doping, which points to the formation of a stable exohedral metallofullerene peapod.

In situ Raman spectroelectrochemistry has been used to distinguish between thin single-wall carbon nanotubes (SWCNT) and the inner tubes of double-wall carbon nanotubes (DWCNT). The spectroelectrochemical method is based on the different change of the electronic structure of the inner tube in DWCNT and that of SWCNT during electrochemical charging, which is reflected in the Raman spectra. During electrochemical charging the inner tubes of DWCNT exhibit a delayed attenuation of the intensities of their Raman modes as referred to the behavior of SWCNT of similar diameter. The changes are pronounced for the radial breathing mode (RBM), and thus, these modes are diagnostic for the distinction of inner tubes of DWCNT from the thin SWCNT. The different sensitivities of inner and outer tubes to the applied electrochemical charging is a simple analytical tool for differentiation of SWCNT and DWCNT in a mixture. The significance of the proposed method is demonstrated on a commercial DWCNT sample.

C60 fullerene peapods and double-walled carbon nanotubes (DWCNTs) containing highly 13C enriched C60 and inner tubes, respectively, are studied using Raman spectroscopy and in situ Raman spectroelectrochemistry in order to follow the influence of 13C enrichment on the vibrational pattern of these carbon nanostructures. The Raman response of 13C60 after encapsulation in fullerene peapods differs from that of isotope-natural species, (Nat)C60. The Raman A(g)(2) mode of encapsulated 13C60 is upshifted in frequency compared to that of the (Nat)C60 peapods with the same filling factor. The chemical doping of 13C60 peapods (peapod = C(60)@SWCNT) with K-vapor leads to the downshift of the A(g)(2) mode, similar to the case of (Nat)C60 peapods. The 13C60 peapods were successfully transformed into DWCNTs, which confirms high filling of single-walled (SW) CNTs with 13C60. The DWCNTs exhibited distinctly downshifted G and D Raman modes for inner tubes, which proves that only inner tubes were enriched by 13C. The in situ Raman spectroelectrochemistry of (Nat)C60 exhibits strong anodic enhancement, while for 13C60 peapods the enhancement is only weak. On the other hand, the electrochemical charging of the inner-tube-labeled DWCNTs (13C(i)-DWCNTs) followed the behavior of ordinary (Nat)C(i)-DWCNTs as indicated by in situ Raman spectroelectrochemistry. In addition, the spectroelectrochemical behavior of the G mode of inner tubes in 13C(i)-DWCNTs is followed from the start of the electrochemical doping, which was not feasible for (Nat)C(i)-DWCNTs.

Raman and in situ Raman spectroelectrochemical studies of Dy3N@C80@SWCNT peapods have been carried out for the first time. The formation of peapods by the encapsulation of gaseous Dy3N@C80 has been confirmed by HR-TEM microscopy and by the successful transformation of Dy3N@C80@SWCNT into double-walled carbon nanotubes. The Raman spectra of the endohedral fullerene cluster changed dramatically in the interior of the single-walled carbon nanotube (SWCNT). The electrochemical charging of the peapod indicates a slight reversible attenuation of the Raman intensities of fullerene features during anodic doping. The results support the assignment of Raman bands to the Dy3N@C80 moiety inside a SWCNT.

In this letter, we show for the first time the use of metal oxides as catalysts in the synthesis of single-walled carbon nanotubes (SWCNTs) using laser ablation. Further, SWCNTs have been synthesized at low temperature (down to room temperature), where their nucleation cannot be explained via fullerene nucleation. The data point to a nucleation mechanism previously not identified, that places a stable oxidized ring as the root cause for the growth of SWCNTs.

In situ ESR, UV-visible, and FT-IR-ATR spectroelectrochemistry were used to study the charge transfer for electrochemically synthesized poly(N,N'-ethylenebis(salicylideneiminato)Cu(II)), which represents a macromolecular metal chelate with ESR-active central metal ions. Structural evidence for different charged states in electroactive poly(Cu(II)-salen) was obtained from ESR, UV-visible, and FT-IR spectra under reversible redox cycling. The changes in a characteristic broad ESR line without hyperfine splitting originating from Cu(II) as well as in the corresponding UV-visible and infrared spectra are discussed in order to describe an electron transfer to the redox-active sites within the polymer chains in detail.