LDH-Based Voltammetric Sensors.

Layered double hydroxides (LDHs), also named hydrotalcite-like compounds, are anionic clays with a lamellar structure which have been extensively used in the last two decades as electrode modifiers for the design of electrochemical sensors. These materials can be classified into LDHs containing or not containing redox-active centers. In the former case, a transition metal cation undergoing a reversible redox reaction within a proper potential window is present in the layers, and, therefore, it can act as electron transfer mediator, and electrocatalyze the oxidation of an analyte for which the required overpotential is too high. In the latter case, a negatively charged species acting as a redox mediator can be introduced into the interlayer spaces after exchanging the anion coming from the synthesis, and, again, the material can display electrocatalytic properties. Alternatively, due to the large specific surface area of LDHs, molecules with electroactivity can be adsorbed on their surface. In this review, the most significant electroanalytical applications of LDHs as electrode modifiers for the development of voltammetric sensors are presented, grouping them based on the two types of materials.

Evaluation of the Antioxidant Capacity of Fruit Juices by Two Original Analytical Methods.

Two analytical methods previously developed by our groups were employed to estimate the antioxidant capacity of commercial fruit juices. The electrochemical method, which measures the scavenging activity of antioxidants towards OH radicals generated by both hydrogen peroxide photolysis and Fenton's reaction, is based on the recovery of the cyclic voltametric response of the redox probe Ru(NH3)63+ at a Glassy Carbon electrode modified with a thin film of an insulating polyphenol, in the presence of compounds with antioxidant properties. The values of the antioxidant capacity of the fruit juices are expressed as vitamin C equivalents/L. The chromatographic method is based on the generation of OH radicals via Fenton's reaction in order to test the inhibition of their formation in the presence of antioxidant compounds by monitoring salicylate aromatic hydroxylation derivatives as markers of •OH production, by means of HPLC coupled to coulometric detection. The results are expressed as the percentage of inhibition of •OH production in the presence of the tested juice compared to the control sample. When OH radicals are produced by Fenton's reaction, the antioxidant capacity of the juices, estimated by both methods, displays an analogous trend, confirming that they can be considered an alternative for measuring the ability of antioxidants to block OH radical formation.

Print-Light-Synthesis for Single-Step Metal Nanoparticle Synthesis and Patterned Electrode Production.

The fabrication of thin-film electrodes, which contain metal nanoparticles and nanostructures for applications in electrochemical sensing as well as energy conversion and storage, is often based on multi-step procedures that include two main passages: (i) the synthesis and purification of nanomaterials and (ii) the fabrication of thin films by coating electrode supports with these nanomaterials. The patterning and miniaturization of thin film electrodes generally require masks or advanced patterning instrumentation. In recent years, various approaches have been presented to integrate the spatially resolved deposition of metal precursor solutions and the rapid conversion of the precursors into metal nanoparticles. To achieve the latter, high intensity light irradiation has, in particular, become suitable as it enables the photochemical, photocatalytical, and photothermal conversion of the precursors during or slightly after the precursor deposition. The conversion of the metal precursors directly on the target substrates can make the use of capping and stabilizing agents obsolete. This review focuses on hybrid platforms that comprise digital metal precursor ink printing and high intensity light irradiation for inducing metal precursor conversions into patterned metal and alloy nanoparticles. The combination of the two methods has recently been named Print-Light-Synthesis by a group of collaborators and is characterized by its sustainability in terms of low material consumption, low material waste, and reduced synthesis steps. It provides high control of precursor loading and light irradiation, both affecting and improving the fabrication of thin film electrodes.

From Traditional to New Benchmark Catalysts for CO2 Electroreduction.

In the last century, conventional strategies pursued to reduce or convert CO2 have shown limitations and, consequently, have been pushing the development of innovative routes. Among them, great efforts have been made in the field of heterogeneous electrochemical CO2 conversion, which boasts the use of mild operative conditions, compatibility with renewable energy sources, and high versatility from an industrial point of view. Indeed, since the pioneering studies of Hori and co-workers, a wide range of electrocatalysts have been designed. Starting from the performances achieved using traditional bulk metal electrodes, advanced nanostructured and multi-phase materials are currently being studied with the main goal of overcoming the high overpotentials usually required for the obtainment of reduction products in substantial amounts. This review reports the most relevant examples of metal-based, nanostructured electrocatalysts proposed in the literature during the last 40 years. Moreover, the benchmark materials are identified and the most promising strategies towards the selective conversion to high-added-value chemicals with superior productivities are highlighted.

Focus Review on Nanomaterial-Based Electrochemical Sensing of Glucose for Health Applications.

Diabetes management can be considered the first paradigm of modern personalized medicine. An overview of the most relevant advancements in glucose sensing achieved in the last 5 years is presented. In particular, devices exploiting both consolidated and innovative electrochemical sensing strategies, based on nanomaterials, have been described, taking into account their performances, advantages and limitations, when applied for the glucose analysis in blood and serum samples, urine, as well as in less conventional biological fluids. The routine measurement is still largely based on the finger-pricking method, which is usually considered unpleasant. In alternative, glucose continuous monitoring relies on electrochemical sensing in the interstitial fluid, using implanted electrodes. Due to the invasive nature of such devices, further investigations have been carried out in order to develop less invasive sensors that can operate in sweat, tears or wound exudates. Thanks to their unique features, nanomaterials have been successfully applied for the development of both enzymatic and non-enzymatic glucose sensors, which are compliant with the specific needs of the most advanced applications, such as flexible and deformable systems capable of conforming to skin or eyes, in order to produce reliable medical devices operating at the point of care.

Smart Bandaid Integrated with Fully Textile OECT for Uric Acid Real-Time Monitoring in Wound Exudate.

Hard-to-heal wounds (i.e., severe and/or chronic) are typically associated with particular pathologies or afflictions such as diabetes, immunodeficiencies, compression traumas in bedridden people, skin grafts, or third-degree burns. In this situation, it is critical to constantly monitor the healing stages and the overall wound conditions to allow for better-targeted therapies and faster patient recovery. At the moment, this operation is performed by removing the bandages and visually inspecting the wound, putting the patient at risk of infection and disturbing the healing stages. Recently, new devices have been developed to address these issues by monitoring important biomarkers related to the wound health status, such as pH, moisture, etc. In this contribution, we present a novel textile chemical sensor exploiting an organic electrochemical transistor (OECT) configuration based on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) for uric acid (UA)-selective monitoring in wound exudate. The combination of special medical-grade textile materials provides a passive sampling system that enables the real-time and non-invasive analysis of wound fluid: UA was detected as a benchmark analyte to monitor the health status of wounds since it represents a relevant biomarker associated with infections or necrotization processes in human tissues. The sensors proved to reliably and reversibly detect UA concentration in synthetic wound exudate in the biologically relevant range of 220-750 µM, operating in flow conditions for better mimicking the real wound bed. This forerunner device paves the way for smart bandages integrated with real-time monitoring OECT-based sensors for wound-healing evaluation.

Synthesis of TiO2 Nanobelt Bundles Decorated with TiO2 Nanoparticles and Aggregates and Their Use as Anode Materials for Lithium-Ion Batteries.

TiO2 nanobelt bundles decorated with TiO2 aggregates were prepared using an easy and scalable hydrothermal method at various temperatures (170, 190, 210, and 230 °C). It was demonstrated that the synthesis temperature is a key parameter to tune the number of aggregates on the nanobelt surface. Prepared TiO2 aggregates and nanobelt bundles were used to design anode materials in which the aggregates regulated the pore size and connectivity of the interconnected nanobelt bundle structure. A galvanostatic technique was employed for the electrochemical characterization of TiO2 samples. Using TiO2 as a model material due to its small volume change during the cycling of lithium-ion batteries (LIBs), the relationship between the morphology of the anode materials and the capacity retention of the LIBs on cycling is discussed. It was clearly found that the size and connectivity of the pores and the specific surface area had a striking impact on the Li insertion behavior, lithium storage capability, and cycling performance of the batteries. The initial irreversible capacity was shown to increase as the specific surface area increased. As the pore size increased, the ability of the mesoporous anatase to release strain was stronger, resulting in better cycling stability. The TiO2 powder prepared at a temperature of 230 °C displayed the highest discharge and charge capacities (203.3 mAh/g and 140.8 mAh/g) and good cycling stability.

ALP-Based Biosensors Employing Electrodes Modified with Carbon Nanomaterials for Pesticides Detection.

Due to the growing presence of pesticides in the environment and in food, the concern of their impact on human health is increasing. Therefore, the development of fast and reliable detection methods is needed. Enzymatic inhibition-based biosensors represent a good alternative for replacing the more complicated and time-consuming traditional methods (chromatography, spectrophotometry, etc.). This paper describes the development of an electrochemical biosensor exploiting alkaline phosphatase as the biological recognition element and a chemically modified glassy carbon electrode as the transducer. The biosensor was prepared modifying the GCE surface by a mixture of Multi-Walled-Carbon-Nanotubes (MWCNTs) and Electrochemically-Reduced-Graphene-Oxide (ERGO) followed by the immobilization of the enzyme by cross-linking with bovine serum albumin and glutaraldehyde. The inhibition of the biosensor response caused by pesticides was established using 2-phospho-L-ascorbic acid as the enzymatic substrate, whose dephosphorylation reaction produces ascorbic acid (AA). The MWCNTs/ERGO mixture shows a synergic effect in terms of increased sensitivity and decreased overpotential for AA oxidation. The response of the biosensor to the herbicide 2,4-dichloro-phenoxy-acetic-acid was evaluated and resulted in the concentration range 0.04-24 nM, with a limit of the detection of 16 pM. The determination of other pesticides was also achieved. The re-usability of the electrode was demonstrated by performing a washing procedure.

Nanoparticles of Mixed-Valence Oxides MnXCO3-XO4 (0 ≤ X ≤ 1) Obtained with Agar-Agar from Red Algae (Rhodophyta) for Oxygen Evolution Reaction.

The development of efficient electrocatalysts for the oxygen evolution reaction (OER) is of paramount importance in sustainable water-splitting technology for hydrogen production. In this context, this work reports mixed-valence oxide samples of the MnXCo3-XO4 type (0 ≤ X ≤ 1) synthesized for the first time by the proteic sol-gel method using Agar-Agar as a polymerizing agent. The powders were calcined at 1173 K, characterized by FESEM, XRD, RAMAN, UV-Vis, FT-IR, VSM, and XPS analyses, and were investigated as electrocatalysts for the oxygen evolution reaction (OER). Through XRD analysis, it was observed that the pure cubic phase was obtained for all samples. The presence of Co3+, Co2+, Mn2+, Mn3+, and Mn4+ was confirmed by X-ray spectroscopy (XPS). Regarding the magnetic measurements, a paramagnetic behavior at 300 K was observed for all samples. As far as OER is concerned, it was investigated in an alkaline medium, where the best overpotential of 299 mV vs. RHE was observed for the sample (MnCo2O4), which is a lower value than those of noble metal electrocatalysts in the literature, together with a Tafel slope of 52 mV dec-1, and excellent electrochemical stability for 15 h. Therefore, the green synthesis method presented in this work showed great potential for obtaining electrocatalysts used in the oxygen evolution reaction for water splitting.

A Wearable Electrochemical Gas Sensor for Ammonia Detection.

The next future strategies for improved occupational safety and health management could largely benefit from wearable and Internet of Things technologies, enabling the real-time monitoring of health-related and environmental information to the wearer, to emergency responders, and to inspectors. The aim of this study is the development of a wearable gas sensor for the detection of NH3 at room temperature based on the organic semiconductor poly(3,4-ethylenedioxythiophene) (PEDOT), electrochemically deposited iridium oxide particles, and a hydrogel film. The hydrogel composition was finely optimised to obtain self-healing properties, as well as the desired porosity, adhesion to the substrate, and stability in humidity variations. Its chemical structure and morphology were characterised by infrared spectroscopy and scanning electron microscopy, respectively, and were found to play a key role in the transduction process and in the achievement of a reversible and selective response. The sensing properties rely on a potentiometric-like mechanism that significantly differs from most of the state-of-the-art NH3 gas sensors and provides superior robustness to the final device. Thanks to the reliability of the analytical response, the simple two-terminal configuration and the low power consumption, the PEDOT:PSS/IrOx Ps/hydrogel sensor was realised on a flexible plastic foil and successfully tested in a wearable configuration with wireless connectivity to a smartphone. The wearable sensor showed stability to mechanical deformations and good analytical performances, with a sensitivity of 60 ± 8 µA decade-1 in a wide concentration range (17-7899 ppm), which includes the safety limits set by law for NH3 exposure.

Nanostructured Copper-Based Electrodes Electrochemically Synthesized on a Carbonaceous Gas Diffusion Membrane with Catalytic Activity for the Electroreduction of CO2.

In this work, four different 4 cm2-sized nanostructured Cu-based electrocatalysts have been designed by a one-step electrodeposition process of Cu metal on a three-dimensional carbonaceous membrane. One consisted of Cu0, and the other three were obtained by further simple oxidative treatments. Morphological, structural, and electrochemical investigations on the four materials were carried out by scanning electron microscopy, Raman spectroscopy, X-ray diffraction, linear sweep voltammetry, and potential-controlled electrolysis. All the electrocatalysts showed promising catalytic activities toward CO2 electroreduction in liquid phase, with a remarkable selectivity toward acetic acid achieved when using the oxidized materials. In particular, the best electrocatalytic activity was observed for the Cu2O-Cu0 catalyst, working at a relatively low potential (-0.4 V vs RHE), which exhibited a stable and low current density of 0.46 mA cm-2 and a productivity of 308 µmol gcat-1 h-1. These results were attributed to the nanostructured morphology that is characterized by many void spaces and by a high surface area, which should guarantee a large number of CuI and Cu0 catalytic active sites. Moreover, kinetic analyses and preliminary studies about catalyst regeneration highlighted the stability of the best-performing catalyst.

Advanced Wound Dressing for Real-Time pH Monitoring.

The rapid evolution of wearable technologies is giving rise to a strong push for textile chemical sensors design targeting the real-time collection of vital parameters for improved healthcare. Among the most promising applications, monitoring of nonhealing wounds is a scarcely explored medical field that still lacks quantitative tools for the management of the healing process. In this work, a smart bandage is developed for the real-time monitoring of wound pH, which has been reported to correlate with the healing stages, thus potentially giving direct access to the wound status without disturbing the wound bed. The fully textile device is realized by integrating a sensing layer, including the two-terminal pH sensor made of a semiconducting polymer and iridium oxide particles, and an absorbent layer ensuring the delivery of a continuous wound exudate flow across the sensor area. The two-terminal sensor exhibits a reversible response with a sensitivity of (59 ± 4) µA pH-1 in the medically relevant pH range for wound monitoring (pH 6-9), and its performance is not substantially affected either by the presence of the most common chemical interferents or by temperature gradients from 22 to 40 °C. Thanks to the robust sensing mechanism based on potentiometric transduction and the simple device geometry, the fully assembled smart bandage was successfully validated in flow analysis using synthetic wound exudate.

Synthesis and Characterization of Layered Double Hydroxides as Materials for Electrocatalytic Applications.

Layered double hydroxides (LDHs) are anionic clays which have found applications in a wide range of fields, including electrochemistry. In such a case, to display good performances they should possess electrical conductivity which can be ensured by the presence of metals able to give reversible redox reactions in a proper potential window. The metal centers can act as redox mediators to catalyze reactions for which the required overpotential is too high, and this is a key aspect for the development of processes and devices where the control of charge transfer reactions plays an important role. In order to act as redox mediator, a material can be present in solution or supported on a conductive support. The most commonly used methods to synthesize LDHs, referring both to bulk synthesis and in situ growth methods, which allow for the direct modification of conductive supports, are here summarized. In addition, the most widely used techniques to characterize the LDHs structure and morphology are also reported, since their electrochemical performance is strictly related to these features. Finally, some electrocatalytic applications of LDHs, when synthesized as nanomaterials, are discussed considering those related to sensing, oxygen evolution reaction, and other energy issues.

Different Electrochemical Sensor Designs Based on Diazonium Salts and Gold Nanoparticles for Pico Molar Detection of Metals.

We report a comparison of sensors' performance of different hybrid nanomaterial architectures modifying an indium tin oxide (ITO) electrode surface. Diazonium salts and gold nanoparticles (AuNPs) were used as building units to design hybrid thin films of successive layers on the ITO electrode surface. Different architectures of hybrid thin films were prepared and characterized with different techniques, such as TEM, FEG-SEM, XPS, and EIS. The prepared electrodes were used to fabricate sensors for heavy metal detection and their performances were investigated using the square wave voltammetry (SWV) method. The comparison of the obtained results shows that the deposition of AuNPs on the ITO surface, and their subsequent functionalization by diazonium salt, is the best performing architecture achieving a high sensitivity in terms of the lower detection limit of pico molar.

Needle-type organic electrochemical transistor for spatially resolved detection of dopamine.

In this work, the advantages of carbon nanoelectrodes (CNEs) and orgonic electrochemical transistors (OECTs) were merged to realise nanometre-sized, spearhead OECTs based on single- and double-barrel CNEs functionalised with a conducting polymer film. The needle-type OECT shows a high aspect ratio that allows its precise positioning by means of a macroscopic handle and its size is compatible with single-cell analysis. The device was characterised with respect to its electrolyte-gated behaviour and was employed as electrochemical sensor for the proof-of-concept detection of dopamine (DA) over a wide concentration range (10-12-10-6 M). Upon application of fixed drain and gate voltages (Vd = - 0.3 V, Vg = - 0.9 V, respectively), the nano-sized needle-type OECT sensor exhibited a linear response in the low pM range and from 0.002 to 7 µM DA, with a detection limit of 1 × 10-12 M. Graphical abstract.

Layered Double Hydroxide-Modified Organic Electrochemical Transistor for Glucose and Lactate Biosensing.

Biosensors based on Organic Electrochemical Transistors (OECTs) are developed for the selective detection of glucose and lactate. The transistor architecture provides signal amplification (gain) with respect to the simple amperometric response. The biosensors are based on a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) channel and the gate electrode is functionalised with glucose oxidase (GOx) or lactate oxidase (LOx) enzymes, which are immobilised within a Ni/Al Layered Double Hydroxide (LDH) through a one-step electrodeposition procedure. The here-designed OECT architecture allows minimising the required amount of enzyme during electrodeposition. The output signal of the biosensor is the drain current (Id), which decreases as the analyte concentration increases. In the optimised conditions, the biosensor responds to glucose in the range of 0.1-8.0 mM with a limit of detection (LOD) of 0.02 mM. Two regimes of proportionality are observed. For concentrations lower than 1.0 mM, a linear response is obtained with a mean gain of 360, whereas for concentrations higher than 1.0 mM, Id is proportional to the logarithm of glucose concentration, with a gain of 220. For lactate detection, the biosensor response is linear in the whole concentration range (0.05-8.0 mM). A LOD of 0.04 mM is reached, with a net gain equal to 400.

Organic Electrochemical Transistors as Versatile Analytical Potentiometric Sensors.

Potentiometric transduction is an important tool of analytical chemistry to record chemical signals, but some constraints in the miniaturization and low-cost fabrication of the reference electrode are a bottleneck in the realization of more-advanced devices such as wearable and lab-on-a-chip sensors. Here, an organic electrochemical transistor (OECT) has been designed with an alternative architecture that allows to record the potentiometric signals of gate electrodes, which have been chemically modified to obtain Ag/AgnX interfaces (X = Cl-, Br-, I-, and S2-), without the use of a reference electrode. When the OECT is immersed in a sample solution, it reaches an equilibrium state, because PEDOT:PSS exchanges charges with the electrolyte until its Fermi level is aligned to the one of Ag/AgnX. The latter is controlled by Xn- concentration in the solution. As a consequence, in this spontaneous process, the conductivity of PEDOT:PSS changes with the electrochemical potential of the modified gate electrode without any external bias. The sensor works by applying only a fixed drain current or drain voltage and thus the OECT sensor operates with just two terminals. It is also demonstrated that, in this configuration, gate potential values extracted from the drain current are in good agreement with the ones measured with respect to a reference electrode being perfectly correlated (linear slope equal to 1.00 ± 0.03). In the case of the sulfide anion, the OECT performance overcomes the limit represented by the Nernst equation, with a sensitivity of 0.52 V decade-1. The presented results suggest that OECTs could be a viable option to fabricate advanced sensors based on potentiometric transduction.

Electrochemical Approach for the Production of Layered Double Hydroxides with a Well-Defined Co/MeIII Ratio.

Layered double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, the electrochemical approach does not usually allow for a fine control of the MII /MIII ratio in the synthesized material. By employing a recently proposed potentiodynamic method, LDH films of controlled composition are herein prepared with good reproducibility, using different ratios of the trivalent (Fe or Al) to bivalent (Co) cations in the electrolytic solution. All the obtained materials are shown to be effective oxygen evolution reaction (OER) catalysts, and are thoroughly characterized by a multi-technique approach, including FE-SEM, XRD, Raman, AES and a wide range of electrochemical procedures.

Electrochemical Deposition of Nanomaterials for Electrochemical Sensing.

The most commonly used methods to electrodeposit nanomaterials on conductive supports or to obtain electrosynthesis nanomaterials are described. Au, layered double hydroxides (LDHs), metal oxides, and polymers are the classes of compounds taken into account. The electrochemical approach for the synthesis allows one to obtain nanostructures with well-defined morphologies, even without the use of a template, and of variable sizes simply by controlling the experimental synthesis conditions. In fact, parameters such as current density, applied potential (constant, pulsed or ramp) and duration of the synthesis play a key role in determining the shape and size of the resulting nanostructures. This review aims to describe the most recent applications in the field of electrochemical sensors of the considered nanomaterials and special attention is devoted to the analytical figures of merit of the devices.

Silica modification of titania nanoparticles enhances photocatalytic production of reactive oxygen species without increasing toxicity potential in vitro.

Titania (TiO2) nanoparticles were surface modified using silica and citrate to implement a 'safe-by-design' approach for managing potential toxicity of titania nanoparticles by controlling surface redox reactivity. DLS and zeta-potential analyses confirmed the surface modification, and electron microscopy and surface area measurements demonstrated nanoscale dimensions of the particles. Electron paramagnetic resonance (EPR) was used to determine the exogenous generation of reactive oxygen species (ROS). All the produced spray dried nanotitania lowered levels of ROS when compared to the corresponding dispersed nanotitania, suggesting that the spray drying process is an appropriate design strategy for the control of nano TiO2 ROS reactivity. The modification of nanotitania with silica and with citrate resulted in increased levels of ROS generation in exogenous measurements, including photoexcitation for 60 minutes. The dichlorodihydrofluorescein (DCFH) assay of dose-dependent production of oxidative stress, generated by pristine and modified nanotitania in macrophages and alveolar epithelial cells, found no significant change in toxicity originating from the generation of reactive oxygen species. Our findings show that there is no direct correlation between the photocatalytic activity of nanotitania and its oxidative stress-mediated potential toxicity, and it is possible to improve the former, for example adding silica as a modifying agent, without altering the cell redox equilibrium.