New Insights into the Surfactant-Assisted Liquid-Phase Exfoliation of Bi2S3 for Electrocatalytic Applications

During water electrolysis, adding an electrocatalyst for the hydrogen evolution reaction (HER) is necessary to reduce the activation barrier and thus enhance the reaction rate. Metal chalcogenide-based 2D nanomaterials have been studied as an alternative to noble metal electrocatalysts because of their interesting electrocatalytic properties and low costs of production. However, the difficulty in improving the catalytic efficiency and industrializing the synthetic methods have become a problem in the potential application of these species in electrocatalysis. Liquid-phase exfoliation (LPE) is a low-cost and scalable technique for lab- and industrial-scale synthesis of 2D-material colloidal inks. In this work, we present, to the best of our knowledge, for the first time a systematic study on the surfactant-assisted LPE of bulk Bi2S3 crystalline powder to produce nanosheets (NSs). Different dispersing agents and LPE conditions have been tested in order to obtain colloidal low-dimensional Bi2S3 NSs in H2O at optimized concentrations. Eventually, colloidally stable layered nano-sized Bi2S3 suspensions can be produced with yields of up to ~12.5%. The thus obtained low-dimensional Bi2S3 is proven to be more active for HER than the bulk starting material, showing an overpotential of only 235 mV and an optimized Tafel slope of 125 mV/dec. Our results provide a facile top-down method to produce nano-sized Bi2S3 through a green approach and demonstrate that this material can have a good potential as electrocatalyst for HER

Assessing the Effect of Stabilization and Carbonization Temperatures on Electrochemical Performance of Electrospun Carbon Nanofibers from Polyacrylonitrile

Supercapacitors (SCs) are considered a promising alternative to batteries to power up portable and wearable devices. Among different categories of materials for SCs, carbon nanofibers (CNFs) are particularly appealing for their electrochemical, morphological, and mechanical properties, coupled with the ease of synthesis. Electrospinning is a simple and low-cost technique to prepare the polymer-based precursors for CNFs, allowing to obtain fibers with a tunable morphology and a diameter in the nanometer range. However, even if electrospun CNFs were intensely studied over the years, in the literature there is a lack of information regarding the optimization of the thermal treatment to prepare bare CNFs with high specific capacitance (C s). Herein, a systematic study on the optimization of the stabilization and carbonization temperatures for electrospun CNFs prepared from polyacrylonirtile is reported, achieving a maximum C s of 49 F g−1 at 0.5 A g−1 in a symmetrical SC device based on 1 m H2SO4 electrolyte. Aspects related to the specific surface area, nitrogen doping, and carbon microstructure are examined concerning the different thermal treatments, allowing to define structure–property–function relationships in these capacitive nanoarchitectures

Near-Infrared Schottky Silicon Photodetectors Based on Two Dimensional Materials

Since its discovery in 2004, graphene has attracted the interest of the scientific community due to its excellent properties of high carrier mobility, flexibility, strong light-matter interaction and broadband absorption. Despite of its weak light optical absorption and zero band gap, graphene has demonstrated impressive results as active material for optoelectronic devices. This success pushed towards the investigation of new two-dimensional (2D) materials to be employed in a next generation of optoelectronic devices with particular reference to the photodetectors. Indeed, most of 2D materials can be transferred on many substrates, including silicon, opening the path to the development of Schottky junctions to be used for the infrared detection. Although Schottky near-infrared silicon photodetectors based on metals are not a new concept in literature the employment of two-dimensional materials instead of metals is relatively new and it is leading to silicon-based photodetectors with unprecedented performance in the infrared regime. This chapter aims, first to elucidate the physical effect and the working principles of these devices, then to describe the main structures reported in literature, finally to discuss the most significant results obtained in recent years

Nanostructured 2D WS2@PANI nanohybrids for electrochemical energy storage

: 2D materials are interesting flat nanoplatforms for the implementation of different electrochemical processes, due to the high surface area and tunable electronic properties. 2D transition metal dichalcogenides (TMDs) can be produced through convenient top-down liquid-phase exfoliation (LPE) methods and present capacitive behaviour that can be exploited for energy storage applications. However, in their thermodynamically stable 2H crystalline phase, they present poor electrical conductivity, being this phase a purely semiconducting one. Combination with conducting polymers like polyaniline (PANI), into nanohybrids, can provide better properties for the scope. In this work, we report on the preparation of 2D WS2@PANI hybrid materials in which we exploit the LPE TMD nanoflakes as scaffolds, onto which induce the in-situ aniline polymerization and thus achieve porous architectures, with the help of surfactants and sodium chloride acting as templating agents. We characterize these species for their capacitive behaviour in neutral pH, achieving maximum specific capacitance of 160 F/g at a current density of 1 A/g, demonstrating the attractiveness of similar nanohybrids for future use in low-cost, easy-to-make supercapacitor devices

Work Function Tuning in Hydrothermally Synthesized Vanadium-Doped MoO3 and Co3O4 Mesostructures for Energy Conversion Devices

The wide interest in developing green energy technologies stimulates the scientific community to seek, for devices, new substitute material platforms with a low environmental impact, ease of production and processing and long-term stability. The synthesis of metal oxide (MO) semiconductors fulfils these requirements and efforts are addressed towards optimizing their functional properties through the improvement of charge mobility or energy level alignment. Two MOs have rising perspectives for application in light harvesting devices, mainly for the role of charge selective layers but also as light absorbers, namely MoO3 (an electron blocking layer) and Co3O4 (a small band gap semiconductor). The need to achieve better charge transport has prompted us to explore strategies for the doping of MoO3 and Co3O4 with vanadium (V) ions that, when combined with oxygen in V2O5, produce a high work function MO. We report on subcritical hydrothermal synthesis of V-doped mesostructures of MoO3 and of Co3O4, in which a tight control of the doping is exerted by tuning the relative amounts of reactants. We accomplished a full analytical characterization of these V-doped MOs that unambiguously demonstrates the incorporation of the vanadium ions in the host material, as well as the effects on the optical properties and work function. We foresee a promising future use of these materials as charge selective materials in energy devices based on multilayer structures

Work Function Tuning in Hydrothermally Synthesized Vanadium-Doped MoO3 and Co3O4 Mesostructures for Energy Conversion Devices

The wide interest in developing green energy technologies stimulates the scientific community to seek, for devices, new substitute material platforms with a low environmental impact, ease of production and processing and long-term stability. The synthesis of metal oxide (MO) semiconductors fulfils these requirements and efforts are addressed towards optimizing their functional properties through the improvement of charge mobility or energy level alignment. Two MOs have rising perspectives for application in light harvesting devices, mainly for the role of charge selective layers but also as light absorbers, namely MoO3 (an electron blocking layer) and Co3O4 (a small band gap semiconductor). The need to achieve better charge transport has prompted us to explore strategies for the doping of MoO3 and Co3O4 with vanadium (V) ions that, when combined with oxygen in V2O5, produce a high work function MO. We report on subcritical hydrothermal synthesis of V-doped mesostructures of MoO3 and of Co3O4, in which a tight control of the doping is exerted by tuning the relative amounts of reactants. We accomplished a full analytical characterization of these V-doped MOs that unambiguously demonstrates the incorporation of the vanadium ions in the host material, as well as the effects on the optical properties and work function. We foresee a promising future use of these materials as charge selective materials in energy devices based on multilayer structures

Bioconjugation of a PNA Probe to Zinc Oxide Nanowires for Label-Free Sensing

Zinc oxide nanowires (ZnONWs) are largely used in biosensing applications due to their large specific surface area, photoluminescence emission and electron mobility. In this work, the surfaces of ZnONWs are modified by covalent bioconjugation of a peptidic nucleic acid (PNA) probe whose sequence is properly chosen to recognize a complementary DNA (cDNA) strand corresponding to a tract of the CD5 mRNA, the main prognostic marker of chronic lymphatic leukemia. The interaction between PNA and cDNA is preliminarily investigated in solution by circular dichroism, CD melting, and polyacrylamide gel electrophoresis. After the immobilization of the PNA probe on the ZnONW surface, we demonstrate the ability of the PNA-functionalized ZnONW platform to detect cDNA in the μM range of concentration by electrical, label-free measurements. The specificity of the sensor is also verified against a non-complementary DNA sequence. These preliminary results highlight the potential application of PNA-bioconjugated ZnONWs to label-free biosensing of tumor markers

Cabbage and fermented vegetables : From death rate heterogeneity in countries to candidates for mitigation strategies of severe COVID-19

Large differences in COVID-19 death rates exist between countries and between regions of the same country. Some very low death rate countries such as Eastern Asia, Central Europe, or the Balkans have a common feature of eating large quantities of fermented foods. Although biases exist when examining ecological studies, fermented vegetables or cabbage have been associated with low death rates in European countries. SARS-CoV-2 binds to its receptor, the angiotensin-converting enzyme 2 (ACE2). As a result of SARS-CoV-2 binding, ACE2 downregulation enhances the angiotensin II receptor type 1 (AT(1)R) axis associated with oxidative stress. This leads to insulin resistance as well as lung and endothelial damage, two severe outcomes of COVID-19. The nuclear factor (erythroid-derived 2)-like 2 (Nrf2) is the most potent antioxidant in humans and can block in particular the AT(1)R axis. Cabbage contains precursors of sulforaphane, the most active natural activator of Nrf2. Fermented vegetables contain many lactobacilli, which are also potent Nrf2 activators. Three examples are: kimchi in Korea, westernized foods, and the slum paradox. It is proposed that fermented cabbage is a proof-of-concept of dietary manipulations that may enhance Nrf2-associated antioxidant effects, helpful in mitigating COVID-19 severity.Peer reviewe

Nrf2-interacting nutrients and COVID-19 : time for research to develop adaptation strategies

There are large between- and within-country variations in COVID-19 death rates. Some very low death rate settings such as Eastern Asia, Central Europe, the Balkans and Africa have a common feature of eating large quantities of fermented foods whose intake is associated with the activation of the Nrf2 (Nuclear factor (erythroid-derived 2)-like 2) anti-oxidant transcription factor. There are many Nrf2-interacting nutrients (berberine, curcumin, epigallocatechin gallate, genistein, quercetin, resveratrol, sulforaphane) that all act similarly to reduce insulin resistance, endothelial damage, lung injury and cytokine storm. They also act on the same mechanisms (mTOR: Mammalian target of rapamycin, PPAR gamma:Peroxisome proliferator-activated receptor, NF kappa B: Nuclear factor kappa B, ERK: Extracellular signal-regulated kinases and eIF2 alpha:Elongation initiation factor 2 alpha). They may as a result be important in mitigating the severity of COVID-19, acting through the endoplasmic reticulum stress or ACE-Angiotensin-II-AT(1)R axis (AT(1)R) pathway. Many Nrf2-interacting nutrients are also interacting with TRPA1 and/or TRPV1. Interestingly, geographical areas with very low COVID-19 mortality are those with the lowest prevalence of obesity (Sub-Saharan Africa and Asia). It is tempting to propose that Nrf2-interacting foods and nutrients can re-balance insulin resistance and have a significant effect on COVID-19 severity. It is therefore possible that the intake of these foods may restore an optimal natural balance for the Nrf2 pathway and may be of interest in the mitigation of COVID-19 severity

Bioconjugation of a PNA Probe to Zinc Oxide Nanowires for Label-Free Sensing

Zinc oxide nanowires (ZnONWs) are largely used in biosensing applications due to their large specific surface area, photoluminescence emission and electron mobility. In this work, the surfaces of ZnONWs are modified by covalent bioconjugation of a peptidic nucleic acid (PNA) probe whose sequence is properly chosen to recognize a complementary DNA (cDNA) strand corresponding to a tract of the CD5 mRNA, the main prognostic marker of chronic lymphatic leukemia. The interaction between PNA and cDNA is preliminarily investigated in solution by circular dichroism, CD melting, and polyacrylamide gel electrophoresis. After the immobilization of the PNA probe on the ZnONW surface, we demonstrate the ability of the PNA-functionalized ZnONW platform to detect cDNA in the μM range of concentration by electrical, label-free measurements. The specificity of the sensor is also verified against a non-complementary DNA sequence. These preliminary results highlight the potential application of PNA-bioconjugated ZnONWs to label-free biosensing of tumor markers