Many different types of materials have been fabricated in the form of nanowires from metals to oxides, other chalcogenides, and inorganic phases [1], as well as carbon or even polymeric materials [2]. However, the fabrication of multicomponent or core-shell nanowires is a more complex task. This has not prevented the pioneering attempts to build heterostructured nanowires of increasing complexity, since the promises of these materials are high. Notable examples of these efforts are the growth of coaxial (p-i-n) silicon nanowires for solar cells and nanoelectronic power systems, [3,4] the formation of atomic metal nanowires inside carbon nanotubes including Mo [5,6] or Cu [7,8], or the electrochemical growth of metals inside TiO₂ nanotubes [9]. In all of these cases, very valuable complex nanomaterials were produced which were nevertheless very elaborate to fabricate.

Along the path to complex materials, a double challenge remains: to prepare more and more complex materials and to do it through simpler and simpler methods. In great contrast with costly physical methods like chemical vapor deposition or molecular beam epitaxy, the bottom-up approach typically associated to the chemical methods provides many opportunities for the development of high-throughput synthesis of nanostructured materials. But as the complexity of the target materials increase, chemical methods tend to be limited by entropy. Fortunately, specific molecular interactions come to the rescue in the form of what we call self-organization or self-assembly.

In our group we have explored the development of complex hybrid materials through this type of approach [10]. Specifically, we have recently carried out synthetic work of hybrids made of silver and biopolymers through matrix chemistry [11], as well as silver and conducting polymers through simple hydrothermal reactions [12,13]. In this way we have recently reported the isolation of ordered Ag@PPy structures we dubbed as ‘nanosnakes’ [12]. Silver or gold are noble metals that are very stable in their metallic form. On the other hand, cheaper but more reactive copper nanostructures are prone to oxidation in air/aqueous solutions. Protection of copper nanoparticles or nanostructures with polymers is an obvious approach to their stabilization. Furthermore, the use of multifunctional conducting polymers for this task could lead to novel materials with built-in multifunctionality. However, attempts to build this type of hybrid materials have been limited to the previous synthesis of Cu nanoparticles followed by coating with PPy which is prepared subsequently and limited to the coating of Cu nanoparticles [14,15].

Figure ​Figure11 shows the representative TEM images of samples obtained as detailed in the experimental procedure (pyrrole 0.2960 g and CuOHCl 0.1995 g) at 150°C for various periods of time. These samples contain a large number of nanocables structures together with abundant globular formations. The high contrast of the nanocable cores suggested their metallic nature, which was confirmed by SAED of an isolated wire. This, together with powder X-ray diffraction of the bulk materials (Figure ​(Figure2)2) ruled out the possibility that the cores could be made of CuOHCl or copper oxides and confirmed the growth of face-centered cubic (fcc) copper. Two diffraction peaks of copper nanocables (Figure ​(Figure2)2) at 2θ=43.26°, 50.46° could be observed clearly from the XRD pattern, which could be indexed as (111) and (200) planes of fcc copper. It should also be remarked that the metallic copper core is single-crystalline in nature as showed by the SAED pattern. The SAED patterns of the marked region from Figure ​Figure1c1c are shown in bottom inset of that figure. The d-spacing calculation was carried out using Equation 1.1, where d is the d-spacing, λ is the wavelength of the electron beam, L is the camera length (in millimeters); the constant (λL) is the camera constant which equals to 22.5 Å mm; and R is radius of the diffraction pattern (in millimeters).

Table ​Table11 shows the d-spacings calculated for the SAED pattern as shown in Figure ​Figure1c1c (inset). It can be seen that the d-spacings for copper fits well with the experimental data, which also agree with the XRD of Cu@PPy (Figure ​(Figure22).

According to the calculation of electron diffraction spots in Figure ​Figure1c1c (inset), it was revealed that the crystal planes spacing of the inner core region were 0.21 nm, 0.187, and 0.125 which corresponded to the crystal plane distances of the main diffraction peaks of copper; the crystal planes are (111), (200), and (220), respectively.

The Fourier transform infrared spectroscopy (FTIR) spectrum of the sample features the peaks characteristic of polypyrrole (Figure ​(Figure3).3). (peaks at 750–780 cm⁻¹ and peak near 800 cm⁻¹ assigned to N-H out of plane bending absorption). The band observed near 950 cm⁻¹ is due to the C-H out of plane bending. The peaks near 1,035 cm⁻¹ are due to the C=C stretching of aromatic compounds. The peak near 1,384 cm⁻¹ corresponds to C-N stretching and C-C vibration. The prominent bands of polypyrrole structure are the aromatic ring vibrations at 1,571 cm⁻¹, C-N in plane deformation at 1,299 cm⁻¹ and C-H in plane vibrations at 1,035 and 950 at 770 cm⁻¹[16]. The C=O band is observed at 1,675 cm⁻¹ which can be assigned to the oxidized pyrrole rings in Cu@PPy. The broad band at 3,300 cm⁻¹ is assigned to O-H stretching vibration. The frequency at 2,910 cm⁻¹ refers to the stretching vibration of the C-H bond [17]. Thus, we conclude that pyrrole was oxidized in situ by CuOHCl, leading to the nanostructures formed by the reaction products, i.e., reduced metallic copper (single-crystalline) and oxidized polypyrrole. The remarkable finding is how this reaction under hydrothermal conditions leads to such a complex and well-ordered nanostructure through a simple synthesis.

The ultraviolet (UV)-vis spectra of the synthesized polypyrrole-coated copper nanocables at liquid phase (pH=6.4) (Figure ​(Figure4)4) show no absorption peaks corresponding to copper particles, which had a characteristic absorption peak at 580 nm [18]. These results agree well with the experimental results obtained, since copper is always detected coated with polypyrrole. The Cu@PPy composites are normally settled down in the reaction vessel. Noteworthy, the UV–vis shows no peaks that could indicate the presence of Cu²⁺-pyrrole complex, which in turn indicates that all the Cu²⁺ ions have reacted with pyrrole at the end of the preparation process.

It should be noted that PPy coats these nanocables very smoothly, but also, that excess PPy forms the conspicuous globular formations. The excess PPy in the form of nanospheres is consistent with the initial composition of the mixture 2:0.78 Py:Cu. We tried to adjust this ratio to optimize the volume fraction of nanocables but found that a 1:1 Py:Cu ratio would not lead to the formation of nanocables. The optimization of synthetic procedures and the isolation of pure nanocables will be the subject of future work.

Concerning the size and shape of the Cu@PPy nanocables, Figure ​Figure11 shows a few of them featuring Cu cores of 290±45 nm wide covered by shells of PPy approximately 130 nm wide. The length of these nanocables is difficult to asset in a statistically meaningful way. However, we have detected with TEM single nanocables as long as 85 μm (600 nm wide) and SEM images show even larger nanocables (Figure ​(Figure55).