Biocompatible rapid few-layers-graphene synthesis in aqueous lignin solutions

Ultrasonic-Assisted Liquid Phase Exfoliation (UALPE) is considered one of the most promising approaches for the scale-up of graphene production. The process is based on the isolation and stabilization of layers of 2D materials, such as graphene: the selection of a proper stabilizing/exfoliating agent is crucial to achieve a stable Few-Layers-Graphene (FLG) dispersion. In the present work we propose the use of alkali lignin (AL) as a polymeric stabilizing agent for the rapid ( ≤3 hours) synthesis of FLG. Sonication time and graphite-to-lignin (Gr/AL) ratios were investigated as the primary operational parameters to identify the optimal working conditions. Spectroscopical characterization of the samples were employed to assess the quality of the synthesized material: the analysis of the Raman and XPS spectra provided insight on the number of layers and the nature of the limited defects introduced with the exfoliation procedure. Low-defectivity FLG was obtained at Gr/AL = 8 and a sonication time of 3 hours. Furthermore, Scan- ning Electron Microscopy and Dynamic Light Scattering were performed to investigate the size of the exfoliated flakes ( ∼400 nm). The procedure proposed represents a rapid route for the synthesis of FLG, which will be further explored for composites in chemiresistive devices

Raman spectroscopy as a tool to investigate the structure and electronic properties of carbon-atom wires

Graphene, nanotubes and other carbon nanostructures have shown potential as candidates for advanced technological applications due to the different coordination of carbon atoms and to the possibility of π-conjugation. In this context, atomic-scale wires comprised of sp-hybridized carbon atoms represent ideal 1D systems to potentially downscale devices to the atomic level. Carbon-atom wires (CAWs) can be arranged in two possible structures: a sequence of double bonds (cumulenes), resulting in a 1D metal, or an alternating sequence of single–triple bonds (polyynes), expected to show semiconducting properties. The electronic and optical properties of CAWs can be finely tuned by controlling the wire length (i.e., the number of carbon atoms) and the type of termination (e.g., atom, molecular group or nanostructure). Although linear, sp-hybridized carbon systems are still considered elusive and unstable materials, a number of nanostructures consisting of sp-carbon wires have been produced and characterized to date. In this short review, we present the main CAW synthesis techniques and stabilization strategies and we discuss the current status of the understanding of their structural, electronic and vibrational properties with particular attention to how these properties are related to one another. We focus on the use of vibrational spectroscopy to provide information on the structural and electronic properties of the system (e.g., determination of wire length). Moreover, by employing Raman spectroscopy and surface enhanced Raman scattering in combination with the support of first principles calculations, we show that a detailed understanding of the charge transfer between CAWs and metal nanoparticles may open the possibility to tune the electronic structure from alternating to equalized bonds

MICROWAVE-ASSISTED BRUCITE AND TALC REACTIONS WITH CO2 AS A PROXY FOR CARBON CAPTURE AND STORAGE BY SERPENTINE

In the last decades many studies have been focusing on Carbon Capture and Storage (CCS) to find a possible remedy to reduce the large increase of anthropogenic carbon dioxide (CO ). Mineral Carbonation (MC) is a potential solution for almost irreversible chemical long-term CCS. It concerns the combination of CaO and MgO with CO forming spontaneously and exothermically dolomite and magnesite. However, kinetic barriers pose sever limitations for the practical exploitation of this reaction. High fractions of MgO are available in silicates such as olivine, orthopyroxene, clinopyroxene and serpentine. To date, data reported that serpentine polymorphs, above all antigorite, is an excellent candidate for fixing the CO as the reaction efficiency is approximately 92% compared to lizardite (40%) and olivine (66%). This is due to the surface reactivity of approximately 18.7 m /g for the dehydrated antigorite compared to10.8 m /g for dehydrated lizardite and 4.6 m /g for olivine. The microwave assisted process for CCS is an innovative technology that can be employed to catalyze the reaction through thermal and non-thermal mechanisms. Some pioneering tests of direct carbonation by microwave hydrothermal equipment have been performed on olivine, lizardite and chrysotile powders [1] but not on antigorite. The structure of serpentine is characterized by corrugated stacked layers of silica and brucite. For this reason, MC involves dissolution of SiO layers, dissolution/dehydration of Mg(OH) layers, and precipitation of magnesium carbonate. To address the chemical response of the single phases, experiments have been performed by both a local microwave-source acting locally on a specific crystal surface and a volume source interacting with an ensemble of grains on synthetic powders and single crystals of pure brucite and talc. In a second step, treatments have been extended to chrysotile, lizardite and antigorite. A characterization of the mechanism and kinetics were performed by scanning probe microscopy on the surface of single crystals phases, supported by Raman spectroscopy and by Scanning and Transmission Electron Microscopy study performed on micro- and nano-sized grains. [1] White, et al. Reaction mechanisms of magnesium silicates with carbon dioxide in microwave fields. Final Report to the U.S. Department ofEnergy, National Energy Technology Laboratory (2004

A Combined Raman Spectroscopy and Atomic Force Microscopy System for In Situ and Real-Time Measures in Electrochemical Cells

: An innovative and versatile set-up for in situ and real time measures in an electrochemical cell is described. An original coupling between micro-Raman spectroscopy and atomic force microscopy enables one to collect data on opaque electrodes. This system allows for the correlation of topographic images with chemical maps during the charge exchange occurring in oxidation/reduction processes. The proposed set-up plays a crucial role when reactions, both reversible and non-reversible, are studied step by step during electrochemical reactions and/or when local chemical analysis is required

Persistent peri-Heptacene: Synthesis and In Situ Characterization

n-peri-Acenes (n-PAs) have gained interest as model systems of zigzag-edged graphene nanoribbons for potential applications in nanoelectronics and spintronics. However, the synthesis of n-PAs larger than peri-tetracene remains challenging because of their intrinsic open-shell character and high reactivity. Presented here is the synthesis of a hitherto unknown n-PA, that is, peri-heptacene (7-PA), in which the reactive zigzag edges are kinetically protected with eight 4-tBu-C6H4 groups. The formation of 7-PA is validated by high-resolution mass spectrometry and in situ FT-Raman spectroscopy. 7-PA displays a narrow optical energy gap of 1.01 eV and exhibits persistent stability (t1/2≈25 min) under inert conditions. Moreover, electron-spin resonance measurements and theoretical studies reveal that 7-PA exhibits an open-shell feature and a significant tetraradical character. This strategy could be considered a modular approach for the construction of next-generation (3 N+1)-PAs (where N≥3). © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH Gmb

Nonlinear Optical Properties of Polyynes: An Experimental Prediction for Carbyne

We present the experimental determination of the vibrational contribution to molecular second hyperpolarizability (Îvib) of very long polyynes that have been recently made available thanks to progress in chemical synthesis. Based on a simple theoretical model, the available experimental data allow estimating the asymptotic behavior of the vibrational contribution to molecular hyperpolarizability for increasing chain length

Synthesis of Zigzag- and Fjord-Edged Nanographene with Dual Amplified Spontaneous Emission

We report the synthesis of a dibenzodinaphthocoronene (DBDNC) derivative as a novel nanographene with armchair, zigzag, and fjord edges, which was characterized by NMR and X-ray crystallography as well as infrared (IR) and Raman spectroscopies. Ultrafast transient absorption (TA) spectroscopy revealed the presence of stimulated emission signals at 655 nm and 710 nm with a relatively long lifetime, which resulted in dual amplified spontaneous emission (ASE) bands under ns-pulsed excitation, indicating the promise of DBNDC as a near-infrared (NIR) fluorophore for photonics. Our results provide new insight into the design of nanographene with intriguing optical properties by incorporating fjord edges.This work was financially supported by the Okinawa Institute of Science and Technology Graduate University (OIST), the Max Planck Society, JSPS KAKENHI Grant No. JP19K24686, and the European Union’s Horizon 2020 Research and Innovation program under grant agreement no. 101017821 (LIGHT-CAP). G. M. P thanks Fondazione Cariplo (Grant no. 2018-0979) for financial support. Researchers from the University of Alicante acknowledge support from the Spanish Ministerio de Ciencia e Innovación and the European Union (Next Generation EU) through grant no. PID2020-119124RB-I00; and to the Conselleria de Innovación, Universidades y Sociedad Digital de la Comunidad Valenciana (Grant No. AICO/2021/093)

Semiconductor-to-Metal Transition in Carbon-Atom Wires Driven by sp2 Conjugated End Groups

Bis(biphenyl)-capped polyynes are investigated to unveil the modulation of the electronic and optical properties of sp-hybridized carbon-atom wires (CAWs) capped with π-conjugated sp2 end groups. Raman and surface enhanced Raman spectroscopy experiments and density functional theory (DFT) calculations reveal structural changes from polyyne-like with alternating single–triple bonds toward cumulene-like with more equalized bonds as a consequence of the charge transfer occurring when wires interact with metallic nanoparticles. While polyynes have semiconducting electronic properties, a more equalized system tends to a cumulene-like structure characterized by a nearly metallic behavior. The effect of different sp2 end groups in driving a semiconductor-to-metal transition is investigated by DFT calculations on a series of CAWs capped with different terminations. We discuss how the modulation of the structural, electronic, and vibrational properties of the sp-carbon chain toward the metallic wire is not trivial and requires a suitable chemical design of the end group and control of charge transfer. These results provide a guideline for the design of novel sp–sp2 hybrid carbon nanosystems with tunable properties, where graphene-like and polyyne-like domains are closely interconnected. The capability to tune the final electronic or optical response of the material makes these hybrid sp–sp2 systems appealing for a future all-carbon-based science and technology