The development of membranes for nanofiltration with ionic transport properties that combine ionic permeability and selectivity is essential for improving the performance of water desalination or blue energy generation systems [1]. Besides, lab-on-chips using one or a few nano-channels combining ionic and electronic transport could open up a whole field of fundamental explorations in bio-iono-electronics and its potential applications: single-molecule detection, artificial synapses/neurons, .... etc [2]. Within this general framework, our aim is to study the ion transport properties of a bioinspired artificial nano-channel consisting of a single-walled carbon nanotube (SWCNT) inside which a biological ion channel (BIC) is confined. The first phase of this project consists of verifying whether or not it is possible to confine such a channel in a SWCNT. The BIC being studied is gramicidin. It is a small, well-characterised protein having a helicoidal structure when inserted into the cytoplasmic membrane [3]. Its outer ring is particularly hydrophobic and hence should facilitate its insertion into a SWCNT. The SWCNTs used are purified EC-15 eDIPS whose average diameter, i.e. ~2.1-2.2 nm, is expected to be large enough to accommodate the protein in its helicoidal form. The results presented here show that gramicidin strongly interacts with SWCNTs and gets inserted. This outcome is obtained using a range of technics: XRD, Raman, XPS, TEM and Water Sorption Isotherms. Particular emphasis will be made on the use of Water Sorption Isotherms as a powerful tool for characterising confinement in SWCNT.

Recent advancements in materials science have shed light on the potential of exploring hierarchical assemblies of molecules on surfaces, driven by both fundamental and applicative challenges. This field encompasses diverse areas including molecular storage, drug delivery, catalysis, and nanoscale chemical reactions. In this context, the utilization of nanotube templates (NTs) has emerged as promising platforms for achieving advanced one-dimensional (1D) molecular assemblies. NTs offer cylindrical, crystalline structures with high aspect ratios, capable of hosting molecules both externally and internally (Mol@NT). Furthermore, NTs possess a wide array of available diameters, providing tunability for tailored assembly. This review underscores recent breakthroughs in the field of Mol@NT. The first part focuses on the diverse panorama of structural properties in Mol@NT synthesized in the last decade. The advances in understanding encapsulation, adsorption, and ordering mechanisms are detailed. In a second part, the review highlights the physical interactions and photophysics properties of Mol@NT obtained by the confinement of molecules and nanotubes in the van der Waals distance regime. The last part of the review describes potential applicative fields of these 1D heterostructures, providing specific examples in photovoltaics, luminescent materials, and bio-imaging. A conclusion gathers current challenges and perspectives of the field to foster discussion in related communities.

Chromophore are encapsulated into host single-walled carbon nanotubes to create hybrid nano-systems with tunable optical and electronic properties. The interplay between the confined molecules and the host nanotube is a key factor1,2.From Raman spectroscopy and G-band shift measurements, a significant charge transfer from the confined dye to the nanotube is evidenced. A photo-activated electron transfer is also inferred for small diameter (~9 Å) semiconducting and metallic tubes.3 The key parameters that govern the charge transfer are the nanotube diameter and the electron donor or acceptor character of the molecules. The resonance Raman intensities of the confined molecules are strongly affected by applying an external pressure.4Furthermore, photoluminescence intensities of nanotubes are either significantly enhanced or quenched depending on the electron donor or acceptor character of the molecules.5 Indeed, the electron (hole) transfer up (down)-shifts the Fermi level of the nanotubes, modulating the radiative de-excitation efficiency.Therefore, molecule confinement into nanotubes is an interesting strategy for the engineering of new opto-electronic devices.[1] L. Alvarez et al, J. Phys. Chem. C, 119, (2015), 5203−5210[2] Y. Almadori et al, J. Phys. Chem. C; 118, (2014), 19462−19468[3] Y. Almadori et al, Carbon 149, (2019), pp. 772-780 [4] R.S. Alencar et al, Carbon 173 (2021) 163-173[5] R. Chambard et al, Carbon, 186, (2022), 423-430

Dyes are encapsulated into single-walled carbon nanotubes to elaborate hy-brid nano-systems with tunable optical and electronic properties. The physical interaction be-tween the confined molecules and the host nanotube is a key factor1,2.From Raman spectroscopy and G-band shift measurements, a significant charge transfer from the confined dye to the nanotube is evidenced. A photo-activated electron transfer is also inferred for small diameter (~9 Å) semiconducting and metallic tubes.3 The key parameters that govern the charge transfer are the nanotube diameter and the electron donor or acceptor character of the molecules. Furthermore, photoluminescence intensities of nanotubes are either significantly en-hanced or quenched depending on the electron donor or acceptor character of the molecules.5The resonance Raman intensities of the confined molecules are strongly affected by applying an external pressure.4 DFT Calculations clearly allow to account for this effect.Therefore, molecule confinement into nanotubes is an efficient strategy for the engineering of new opto-electronic devices.

We report on the successful synthesis of Bi1−xSbx alloys via mechanical alloying followed by sintering via spark plasma sintering, and the study of their lattice dynamics by Raman spectroscopy as well as their transport and thermoelectric properties. We observed an upshift of the frequency of the Raman-active Eg vibrational mode with increasing Sb content but no significant change for the frequency of the Raman-active A1g vibrational mode. Conversely, the linewidth of the Eg vibrational mode did not change significantly with increasing Sb content, whereas a twofold increase was observed for the A1g vibrational mode. Moreover, we confirm the emergence of several new vibrational modes with Sb alloying that could be associated with Bi-Sb and Sb-Sb vibrations. Rather large magnetoresistance was observed for all samples at room temperature. From the Seebeck coefficients, we determined the energy bandgaps in our samples, which are larger than those in bulk compounds, presumably due to the electronic confinement effect. We report a rather large thermoelectric power factor of 2–3 mW/m.K2 and thermoelectric figure of merit ZT of 0.15–0.23 at room temperature. However, ZT values were not improved at room temperature compared to prior works because of the rather large thermal conductivity of 3.75–4.5 W/m.K at room temperature. We find a larger resistivity, Seebeck coefficient, and power factor for the samples sintered at 200 °C for 5 min than for the samples sintered at 220 °C for 15 min, but similar thermal conductivity, resulting in larger ZT for the samples obtained in the first conditions. The samples with low Sb content x = 0.05 have a lower power factor and larger thermal conductivity than the samples with x = 0.12 and x = 0.15 for the same sintering conditions, which results in lower ZT for x = 0.05.

The development of hybrid nanomaterials that preserve and combine the properties of their constituents is a central issue of nanosciences. Herein, we describe the polymerization via CuAAC (copper-catalyzed azide-alkyne cycloaddition) of cobalt(III) corroles around conductive carbon nanotubes to produce chemically robust hybrid catalysts for Oxygen Reduction Reaction (ORR). A combination of techniques including UV-Vis-NIR absorption, Raman and X-ray Photoelectron Spectroscopy (XPS) as well as Scanning Electron Microscopy (SEM) were used to characterize the assembly of the two parts of the functional hybrid system for which the activity and the selectivity toward the ORR process in acidic media are enlightened by a combination of Rotating Disk Electrode (RDE) and Rotating Ring Disk Electrode (RRDE) measurements. The polymerized hybrid (click MWNT-CoCorr) exhibits an overpotential of ca. 230 mV compared to a reference platinum ink; the number of electrons involved in the reduction of oxygen is close to 3 in acidic media demonstrating that the corrole cobalt centers in the hybrids reduce oxygen via a mix of 2 and 4 electrons pathways.