Interlocking Matrix and Filler for Enhanced Individualization and Reinforcement in Polymer-Single-Walled Carbon Nanotube Composites.

Poor individualization and interfacial adhesion prevent single-walled carbon nanotube (SWNT)-polymer composites from reaching outstanding mechanical properties. With much larger diameters, but common structural features (high aspect ratio and absence of functional groups for covalent or supramolecular attachment with the polymer), carbon fibers face similar problems, which are addressed by covering the fibers with a thin layer of polymer. This sizing strategy has allowed carbon fibers to become the filler of choice for the highest performing materials. Inspired by this, here we investigate the use of the mechanical bond to wrap SWNTs with a layer of polymeric material to produce SWNTs mechanically interlocked with a layer of polymer. We first validate the formation of mechanically interlocked nanotubes (MINTs) using mixtures of SWNTs of relatively large average diameter (1.6 ± 0.4 nm), which are commercially available at reasonable prices and therefore could be technologically relevant as polymer fillers. We then design and synthesize by ring-opening metathesis polymerization (ROMP) a polymer decorated with multiple U-shaped molecules, which are later ring-closed around the SWNTs using metathesis. The obtained hybrids contain a high degree of individualized SWNTs and exhibit significantly increased mechanical properties when compared to the matrix polymer. We envision that this strategy could be employed to produce SWNTs interlocked with polymer layers with various designs for polymer reinforcement.

Direct Magnetic Evidence, Functionalization, and Low-Temperature Magneto-Electron Transport in Liquid-Phase Exfoliated FePS3.

Magnetism and the existence of magnetic order in a material is determined by its dimensionality. In this regard, the recent emergence of magnetic layered van der Waals (vdW) materials provides a wide playground to explore the exotic magnetism arising in the two-dimensional (2D) limit. The magnetism of 2D flakes, especially antiferromagnetic ones, however, cannot be easily probed by conventional magnetometry techniques, being often replaced by indirect methods like Raman spectroscopy. Here, we make use of an alternative approach to provide direct magnetic evidence of few-layer vdW materials, including antiferromagnets. We take advantage of a surfactant-free, liquid-phase exfoliation (LPE) method to obtain thousands of few-layer FePS3 flakes that can be quenched in a solvent and measured in a conventional SQUID magnetometer. We show a direct magnetic evidence of the antiferromagnetic transition in FePS3 few-layer flakes, concomitant with a clear reduction of the Néel temperature with the flake thickness, in contrast with previous Raman reports. The quality of the LPE FePS3 flakes allows the study of electron transport down to cryogenic temperatures. The significant through-flake conductance is sensitive to the antiferromagnetic order transition. Besides, an additional rich spectra of electron transport excitations, including secondary magnetic transitions and potentially magnon-phonon hybrid states, appear at low temperatures. Finally, we show that the LPE is additionally a good starting point for the mass covalent functionalization of 2D magnetic materials with functional molecules. This technique is extensible to any vdW magnetic family.

The Role of Transmission Electron Microscopy in the Early Development of Mesoporous Materials for Tissue Regeneration and Drug Delivery Applications.

For the last 20 years, silica-based mesoporous materials have provided a sound platform for the development of biomedical technology applied to tissue engineering and drug delivery. Their unique structural and textural characteristics, chiefly, the ordered distribution of homogeneous and tunable pores with high surface areas and large pore volume, and their excellent biocompatibility provide an excellent starting point for bone tissue regeneration on the mesoporous surface, and also to load species of interest inside the pores. Adequate control of the synthesis conditions and functionalization of the mesoporous surface are critical factors in the design of new systems that are suitable for use in specific medical applications. Simultaneously, the use of appropriate characterization techniques in the several stages of design and manufacture of mesoporous particles allows us to ascertain the textural, structural and compositional modifications induced during the synthesis, functionalization and post-in vitro assays processes. In this scenario, the present paper shows, through several examples, the role of transmission electron microscopy and associated spectroscopic techniques in the search for useful information in the early design stages of mesoporous systems, with application in the fields of tissue regeneration and drug delivery systems.

Exceptional Low-Temperature CO Oxidation over Noble-Metal-Free Iron-Doped Hollandites: An In-Depth Analysis of the Influence of the Defect Structure on Catalytic Performance.

A family of iron-doped manganese-related hollandites, K x Mn1-y Fe y O2-δ (0 ≤ y ≤ 0.15), with high performance in CO oxidation have been prepared. Among them, the most active catalyst, K0.11Mn0.876Fe0.123O1.80(OH)0.09, is able to oxidize more than 50% of CO at room temperature. Detailed compositional and structural characterization studies, using a wide battery of thermogravimetric, spectroscopic, and diffractometric techniques, both at macroscopic and microscopic levels, have provided essential information about this never-reported behavior, which relates to the oxidation state of manganese. Neutron diffraction studies evidence that the above compound stabilizes hydroxyl groups at the midpoints of the tunnel edges as in isostructural ß-FeOOH. The presence of oxygen and hydroxyl species at the anion sublattice and Mn3+, confirmed by electron energy loss spectroscopy, appears to play a key role in the catalytic activity of this doped hollandite oxide. The analysis of these detailed structural features has allowed us to point out the key role of both OH groups and Mn3+ content in these materials, which are able to effectively transform CO without involving any critical, noble metal in the catalyst formulation.

Ionic Conductivity and Potential Application for Fuel Cell of a Modified Imine-Based Covalent Organic Framework.

We present the novel potential application of imine-based covalent organic frameworks (COFs), formed by the direct Schiff reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde building blocks in m-cresol or acetic acid, named RT-COF-1 or RT-COF-1Ac/RT-COF-1AcB. The post-synthetic treatment of RT-COF-1 with LiCl leads to the formation of LiCl@RT-COF-1. The ionic conductivity of this series of polyimine COFs has been characterized at variable temperature and humidity, using electrochemical impedance spectroscopy. LiCl@RT-COF-1 exhibits a conductivity value of 6.45 × 10-3 S cm-1 (at 313 K and 100% relative humidity) which is among the highest values so far reported in proton conduction for COFs. The mechanism of conduction has been determined using 1H and 7Li solid-state nuclear magnetic resonance spectroscopy. Interestingly, these materials, in the presence of controlled amounts of acetic acid and under pressure, show a remarkable processability that gives rise to quasi-transparent and flexible films showing in-plane structural order as confirmed by X-ray crystallography. Finally, we prove that these films are useful for the construction of proton exchange membrane fuel cells (PEMFC) reaching values up to 12.95 mW cm-2 and 53.1 mA cm-2 for maximum power and current density at 323 K, respectively.

Direct On-Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature.

We report herein an efficient, fast, and simple synthesis of an imine-based covalent organic framework (COF) at room temperature (hereafter, RT-COF-1). RT-COF-1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N2 and CO2 . The room-temperature synthesis has enabled us to fabricate and position low-cost micro- and submicropatterns of RT-COF-1 on several surfaces, including solid SiO2 substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink-jet printing.

A SAED and HREM study of structural defects in brownmillerite, LaBa(x)Sr(1-x)CuGaOy related oxides.

The synthesis and microstructural characterization, by means of selected area electron diffraction (SAED) and high resolution electron microscopy (HREM), of the solid solution LaBa(x)Sr(1-x)CuGaO5 (0.1 < or = 5 x < or = 0.9) is reported. Although an average brownmillerite Ima2 structure is proposed for the whole compositional range, SAED and HREM clearly show that structural defects appear as barium content increases.