1,2-Dimethoxyethane Degradation Thermodynamics in Li-O2 Redox Environments.

The reaction thermodynamics of the 1,2-dimethoxyethane (DME), a model solvent molecule commonly used in electrolytes for Li-O2 rechargeable batteries, has been studied by first-principles methods to predict its degradation processes in highly oxidizing environments. In particular, the reactivity of DME towards the superoxide anion O2- in oxygen-poor or oxygen-rich environments is studied by density functional calculations. Solvation effects are considered by employing a self-consistent reaction field in a continuum solvation model. The degradation of DME occurs through competitive thermodynamically driven reaction paths that end with the formation of partially oxidized final products such as formaldehyde and methoxyethene in oxygen-poor environments and methyl oxalate, methyl formate, 1-formate methyl acetate, methoxy ethanoic methanoic anhydride, and ethylene glycol diformate in oxygen-rich environments. This chemical reactivity indirectly behaves as an electroactive parasitic process and therefore wastes part of the charge exchanged in Li-O2 cells upon discharge. This study is the first complete rationale to be reported about the degradation chemistry of DME due to direct interaction with O2- /O2 molecules. These findings pave the way for a rational development of new solvent molecules for Li-O2 electrolytes.

Assessing the evolution of oxygenated functional groups on the graphene oxide surface upon mild thermal annealing in water.

Graphene oxide (GO) is known to be a 2D metastable nanomaterial that can be reconstructed under thermal annealing into distinct oxidized and graphitic phases. Up to now, such phase transformation, mainly related to epoxide and hydroxyl functional groups, has been usually achieved by thermally treating layers of GO in the solid state. Here, we present the mild annealing of GO dispersed in an aqueous medium, performed at two temperatures, 50 °C and 80 °C, for different intervals of time. We show experimental evidences of the epoxide instability in the presence of water by means of XPS, cyclic voltammetry and Raman spectroscopy, demonstrating the reorganization of epoxide and hydroxyl moieties initiated by water molecules. In fact, at 50 °C an increase in oxygen content is detected in all annealed samples compared to untreated GO, with a transformation of epoxide groups into vicinal diols. On the other hand, at 80 °C the oxygen content decreases towards the initial value since the vicinal diols, previously formed, transform into single hydroxyls and C[double bond, length as m-dash]C bonds. Moreover, the higher temperature annealing likely favours oxygenated functional groups rearrangements and clustering, in accordance with the literature, leading to a higher electron affinity and conductivity of the graphenic network.

Self-Assembling Peptide-Based Magnetogels for the Removal of Heavy Metals from Water.

In this study, we present the synthesis of a novel peptide-based magnetogel obtained through the encapsulation of γ-Fe2O3-polyacrylic acid (PAA) nanoparticles (γ-Fe2O3NPs) into a hydrogel matrix, used for enhancing the ability of the hydrogel to remove Cr(III), Co(II), and Ni(II) pollutants from water. Fmoc-Phe (Fluorenylmethoxycarbonyl-Phenylalanine) and diphenylalanine (Phe2) were used as starting reagents for the hydrogelator (Fmoc-Phe3) synthesis via an enzymatic method. The PAA-coated magnetic nanoparticles were synthesized in a separate step, using the co-precipitation method, and encapsulated into the peptide-based hydrogel. The resulting organic/inorganic hybrid system (γ-Fe2O3NPs-peptide) was characterized with different techniques, including FT-IR, Raman, UV-Vis, DLS, ζ-potential, XPS, FESEM-EDS, swelling ability tests, and rheology. Regarding the application in heavy metals removal from aqueous solutions, the behavior of the obtained magnetogel was compared to its precursors and the effect of the magnetic field was assessed. Four different systems were studied for the separation of heavy metal ions from aqueous solutions, including (1) γ-Fe2O3NPs stabilized with PAA, (γ-Fe2O3NPs); (2) Fmoc-Phe3 hydrogel (HG); (3) γ-Fe2O3NPs embedded in peptide magnetogel (γ-Fe2O3NPs@HG); and (4) γ-Fe2O3NPs@HG in the presence of an external magnetic field. To quantify the removal efficiency of these four model systems, the UV-Vis technique was employed as a fast, cheap, and versatile method. The results demonstrate that both Fmoc-Phe3 hydrogel and γ-Fe2O3NPs peptide magnetogel can efficiently remove all the tested pollutants from water. Interestingly, due to the presence of magnetic γ-Fe2O3NPs inside the hydrogel, the removal efficiency can be enhanced by applying an external magnetic field. The proposed magnetogel represents a smart multifunctional nanosystem with improved absorption efficiency and synergic effect upon applying an external magnetic field. These results are promising for potential environmental applications of γ-Fe2O3NPs-peptide magnetogels to the removal of pollutants from aqueous media.

One-pot carboxyl enrichment fosters water-dispersibility of reduced graphene oxide: a combined experimental and theoretical assessment.

Graphene, one of the allotropic forms of carbon, has attracted enormous interest in the last few years due to its unique properties. Reduced graphene oxide (RGO) is known as the nanomaterial most similar to graphene in terms of electronic, chemical, mechanical, and optical properties. It is prepared from graphene oxide (GO) in the presence of different types of reducing agents. Nevertheless, the application of RGO is still limited, owing to its tendency to irreversibly aggregate in an aqueous medium. Herein, we disclosed the preparation of water-dispersible RGO from GO previously enriched with additional carboxyl functional groups through a one-pot reaction, followed by chemical reduction. This novel and unprecedentedly reported reactivity of GO toward the acylating agent succinic anhydride (SA) was experimentally investigated through XPS, Raman, FT-IR, and UV-Vis, and corroborated by DFT calculations, which have shown a peculiar involvement in the functionalization reaction of both epoxide and hydroxyl functional groups. This proposed synthetic protocol avoids use of sodium cyanide, previously reported for carboxylation of graphene, and focuses on the sustainable and scalable preparation of a water-dispersible RGO, paving the way for its application in many fields where the colloidal stability in aqueous medium is required.

Femtosecond laser-induced nano- and microstructuring of Cu electrodes for CO2 electroreduction in acetonitrile medium.

The dependency of CO2 reduction rate in acetonitrile-Bu4NClO4 solution on cathodes, which were modified by laser induction of a copper surface, was studied. The topography of laser-induced periodic surface structures (LIPSS) → grooves → spikes was successively formed by a certain number of pulses. It was proved that for a higher number of laser pulses, the surface area of the copper cathode increases and preferred platy orientation of the copper surface on [022] crystallografic direction and larger fluence values increase. At the same time, the content of copper (I) oxide on the surface of the copper cathode increases. Also, the tendency to larger fluency values is observed. It promotes the increase of cathodic current density for CO2 reduction, which reaches values of 14 mA cm-2 for samples with spikes surface structures at E = - 3.0 V upon a stable process.

Self-Healing and Reprocessable Oleic Acid-Based Elastomer with Dynamic S-S Bonds as Solvent-Free Reusable Adhesive on Copper Surface.

In the last decade, the application of dynamic covalent chemistry in the field of polymeric materials has become the subject of an increasing number of studies, gaining applicative relevance. This is due to the fact that polymers containing dynamic functions possess a structure that affords reprocessability, recyclability and peculiar self-healing properties inconceivable for "classic" polymer networks. Consequently, the synthesis of a dynamic covalent chemistry-based polymer and its chemical, thermal, and mechanical characterizations are reported in the present research. In particular, oleic acid has been used as starting material to follow the founding principles of the circular economy system and, thanks to the aromatic disulfide component, which is the foundation of the material dynamic characteristics, the obtained polymer resulted as being reprocessable and self-healable. Moreover, the polymer can strongly interact with copper surfaces through the formation of stable Cu-S bonds. Then, the application of the polymer as a solvent-free reusable adhesive for copper was investigated by lap joint shear tests and comparisons with the properties of an analogous material, devoid of the disulfide bonds, were conducted.

Green In Situ Synthesis of Silver Nanoparticles-Peptide Hydrogel Composites: Investigation of Their Antibacterial Activities.

The present paper investigated the synthesis of peptide-based hydrogel composites containing photo-generated silver nanoparticles (AgNPs) obtained in the presence and absence of honey as tensile strength enhancer and hydrogel stabilizer. Fmoc-Phe and diphenylalanine (Phe2) were used as starting reagents for the hydrogelator synthesis via an enzymatic method. In particular, we developed an in situ one-pot approach for preparing AgNPs inside peptide hydrogels using a photochemical synthesis, without any toxic reducing agents, with reaction yields up to 30%. The structure and morphology of the nanohybrids were characterized with different techniques such as FESEM, UV-Vis, DLS, SAXS and XPS. Moreover, the antibacterial activity of these hybrid biomaterials was investigated on a laboratory strain and on a clinical isolate of Staphylococcus aureus. Results demonstrated that honey increased both swelling ability and also mechanical stability of the hydrogel. Finally, a higher antibacterial effect of AgNPs in the hybrid was observed in the presence of honey. In particular, AgNPs/hgel and AgNPs/hgel-honey showed an enhanced antibacterial activity (3.12 mg/L) compared to the free form of AgNPs, alone or in combination with honey (6.25 mg/L) for both S. aureus strains.

Copper protection by self-assembled monolayers of aromatic thiols in alkaline solutions.

Copper corrosion in alkaline solutions is inhibited by the formation of self-assembled monolayers of aromatic thiols, made of either benzenethiol or 2-naphthalenethiol or 4-acetamidothiophenol. Electrochemical experiments, based on voltammetry and impedance spectroscopy, point out the much lower reactivity of copper surfaces towards oxidation, when covered by compact adlayers of the above molecules bonded through the S atom. The peculiar shape and peak position in the voltammetric reduction of residual oxides grown on modified metal surfaces suggest that they are due to Cu(I) suboxides, probably grown on reactive metal defects. XPS experiments have confirmed that the aromatic adlayers are still covering most of the Cu surface even after 1 h immersion in 0.5 M NaOH. The main changes in Auger and XP spectra indicate the formation of much less Cu(2)O in the protected samples than in the corresponding bare Cu aged in NaOH. From the experimental data the presence of defective copper oxides on modified Cu has been deduced.

Progress, highlights and perspectives on NiO in perovskite photovoltaics.

The power conversion efficiency (PCE) of NiO based perovskite solar cells has recently hit a record 22.1% with a hybrid organic-inorganic perovskite composition and a PCE above 15% in a fully inorganic configuration was achieved. Moreover, NiO processing is a mature technology, with different industrially attractive processes demonstrated in the last few years. These considerations, along with the excellent stabilities reported, clearly point towards NiO as the most efficient inorganic hole selective layer for lead halide perovskite photovoltaics, which is the topic of this review. NiO optoelectronics is discussed by analysing the different doping mechanisms, with a focus on the case of alkaline and transition metal cation dopants. Doping allows tuning the conductivity and the energy levels of NiO, improving the overall performance and adapting the material to a variety of perovskite compositions. Furthermore, we summarise the main investigations on the NiO/perovskite interface stability. In fact, the surface of NiO is commonly oxidised and reactive with perovskite, also under the effect of light, thermal and electrical stress. Interface engineering strategies should be considered aiming at long term stability and the highest efficiency. Finally, we present the main achievements in flexible, fully printed and lead-free perovskite photovoltaics which employ NiO as a layer and provide our perspective to accelerate the improvement of these technologies. Overall, we show that adequately doped and passivated NiO might be an ideal hole selective layer in every possible application of perovskite solar cells.

Biocompatible N-acetyl cysteine reduces graphene oxide and persists at the surface as a green radical scavenger.

We demonstrate that N-acetyl cysteine (NAC) reduces graphene oxide (GO) at room temperature. This represents a new green method to produce reduced GO (rGO). NAC adheres to the rGO surface as demonstrated by several spectroscopy techniques and avoids GO-mediated oxidation of glutathione. This method offers new opportunities for the production of green biocompatible rGO and NAC-based therapies.

Electrochemical reversibility of vinylferrocene monolayers covalently attached on H-terminated p-Si(100).

A reversible electrochemical behavior is demonstrated on a specially prepared redox-functionalized H-Si(100) surface, obtained via an extra-mild grafting procedure from vinylferrocene. The results of a detailed XPS and electrochemical characterization of the resulting hybrid are reported and discussed to propose it as a reference system for high-quality electroactive monolayers on Si. The investigated ferrocene derivative bears a functional group suitable for a mild route to covalent anchoring on Si, which is based on a photoinduced reaction with visible light under an inert atmosphere. Electrochemical reversibility is shown by sharp symmetric voltammograms on freshly prepared p-Si electrodes. Anodic oxide growth is responsible for the progressive degradation of the electrochemical response. Still, fast electron transfer to the surface redox species is maintained during several thousands cycles.