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.

Oxygen Gas Sensing Using a Hydrogel-Based Organic Electrochemical Transistor for Work Safety Applications.

Oxygen depletion in confined spaces represents one of the most serious and underestimated dangers for workers. Despite the existence of several commercially available and widely used gas oxygen sensors, injuries and deaths from reduced oxygen levels are still more common than for other hazardous gases. Here, we present hydrogel-based organic electrochemical transistors (OECTs) made with the conducting polymer poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) as wearable and real-time oxygen gas sensors. After comparing OECT performances using liquid and hydrogel electrolytes, we identified the best PEDOT:PSS active layer and hydrogel coating (30 µm) combination for sensing oxygen in the concentration range of 13−21% (v/v), critical for work safety applications. The fast O2 solubilization in the hydrogel allowed for gaseous oxygen transduction in an electrical signal thanks to the electrocatalytic activity of PEDOT:PSS, while OECT architecture amplified the response (gain ~ 104). OECTs proved to have comparable sensitivities if fabricated on glass and thin plastic substrates, (−12.2 ± 0.6) and (−15.4 ± 0.4) µA/dec, respectively, with low power consumption (<40 µW). Sample bending does not influence the device response, demonstrating that our real-time conformable and lightweight sensor could be implemented as a wearable, noninvasive safety tool for operators working in potentially hazardous confined spaces.

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.