Accumulation of Liquid Byproducts in an Electrolyte as a Critical Factor That Compromises Long-Term Functionality of CO2-to-C2H4 Electrolysis.

Electrochemical conversion of CO2 using Cu-based gas diffusion electrodes opens the way to green chemical production as an alternative to thermocatalytic processes and a storage solution for intermittent renewable electricity. However, diverse challenges, including short lifetimes, currently inhibit their industrial usage. Among well-studied determinants such as catalyst characteristics and electrode architecture, possible effects of byproduct accumulation in the electrolyte as an operational factor have not been elucidated. This work quantifies the influence of ethanol, n-propanol, and formate accumulation on selectivity, stability, and cell potential in a CO2-to-C2H4 electrolyzer. Alcohols accelerated flooding by degrading the hydrophobic electrode characteristics, undermining selective and stable ethylene formation. Furthermore, high alcohol concentrations triggered the catalyst layer's abrasion and structural disfigurements in the Nafion 117 membrane, leading to high cell potentials. Therefore, continuous removal of alcohols from the electrolyte medium or substantial modifications in the cell components must be considered to ensure long-term performing CO2-to-C2H4 electrolyzers.

Gas evolution in electrochemical flow cell reactors induces resistance gradients with consequences for the positioning of the reference electrode.

With the transfer of the electrochemical CO2-reduction from academic labs towards industrial application, one major factor is the increase in current density. This can be achieved via the usage of a gas diffusion electrode. It allows for electrochemical reactions at the three-phase boundary between gaseous CO2, liquid electrolyte and electrocatalyst. Thus, current densities in commercially relevant magnitudes of 200 mA cm-2 and beyond can be reached. However, when increasing the current density one faces a new set of challenges, unknown from low current experiments. Here, we address the issue of gas evolution causing a local increase in resistance and the impact on the operation of flow cells with gas diffusion electrodes. We set up a simple simulation model and compared the results with experiments on a real setup. As a result, the gas evolution's strong impact on current-, potential- and resistance-distributions along the flow axis can be described. Main consequence is that the positioning of the reference electrode has a significant effect on the locally measured IR-drop and thus on the measured or applied potential. Therefore, data from different setups must be compared with great care, especially with respect to the potentials, on which the cell is operated.

Automatic Tissue Differentiation Based on Confocal Endomicroscopic Images for Intraoperative Guidance in Neurosurgery.

Diagnosis of tumor and definition of tumor borders intraoperatively using fast histopathology is often not sufficiently informative primarily due to tissue architecture alteration during sample preparation step. Confocal laser microscopy (CLE) provides microscopic information of tissue in real-time on cellular and subcellular levels, where tissue characterization is possible. One major challenge is to categorize these images reliably during the surgery as quickly as possible. To address this, we propose an automated tissue differentiation algorithm based on the machine learning concept. During a training phase, a large number of image frames with known tissue types are analyzed and the most discriminant image-based signatures for various tissue types are identified. During the procedure, the algorithm uses the learnt image features to assign a proper tissue type to the acquired image frame. We have verified this method on the example of two types of brain tumors: glioblastoma and meningioma. The algorithm was trained using 117 image sequences containing over 27 thousand images captured from more than 20 patients. We achieved an average cross validation accuracy of better than 83%. We believe this algorithm could be a useful component to an intraoperative pathology system for guiding the resection procedure based on cellular level information.

Miniaturized sensor for particles in air using Fresnel ring lenses and an enhanced intensity ratio technique.

We present a miniaturized particle sensor collecting scattered light in two solid angle intervals by Fresnel ring lenses. The particle size is determined from the ratio of both scattering amplitudes (intensity ratio) in addition to a linear diversity combining technique, generating a 3D particle size matrix that reduces the ambiguity by the index of refraction on the particle size identification. A signal-to-noise ratio of 30.3 was achieved for 147 nm sized polystyrene latex particles. Measurements of polydisperse particle size distribution show good agreement with the results by a scanning mobility particle sizer.

Half-cell potential analysis of an ammonia sensor with the electrochemical cell Au | YSZ | Au, V2O5-WO3-TiO2.

Half-cell potentials of the electrochemical cell Au, VWT | YSZ | Au are analyzed in dependence on oxygen and ammonia concentration at 550 °C. One of the gold electrodes is covered with a porous SCR catalyst, vanadia-tungstenia-titania (VWT). The cell is utilized as a potentiometric ammonia gas sensor and provides a semi-logarithmic characteristic curve with a high NH3 sensitivity and selectivity. The analyses of the Au | YSZ and Au, VWT | YSZ half-cells are conducted to describe the non-equilibrium behavior of the sensor device in light of mixed potential theory. Both electrode potentials provide a dependency on the NH3 concentration, whereby VWT, Au | YSZ shows a stronger effect which increases with increasing VWT coverage. The potential shifts in the anodic direction confirm the formation of mixed potentials at both electrodes resulting from electrochemical reactions of O2 and NH3 at the three-phase boundary. Polarization curves indicate Butler-Volmer-type kinetics. Modified polarization curves of the VWT covered electrode show an enhanced anodic reaction and an almost unaltered cathodic reaction. The NH3 dependency is dominated by the VWT coverage and it turns out that the catalytic properties of the VWT thick film are responsible for the electrode potential shift.

Using a cell-based gas biosensor for investigation of adverse effects of acetone vapors in vitro.

In this study, a cell-based gas biosensor is presented used for the detection and investigation of gaseous organic compounds in air. The response of living human nasal cells (RPMI 2650) and human lung cells (A549) towards the direct exposure of gaseous substances for 10 min is monitored with a multi-parametric sensor system. Changes in the cellular impedance, oxygen consumption rate and acidification rate can be recorded after the exposure and represent the cytotoxicity of the present gas. The sensor is able to notify the presence of acetone in aqueous solution (2%) but in notably lower concentrations in the gas phase (100-333 ppm) within 30-60 min after the end of the gas exposure. Cell viability is not affected by a sequential exposure to humidified synthetic air (60% r.h.) with a flow rate of 300 ml/min and therefore offers the possibility for a continuous air monitoring. In addition, exposure to synthetic air has no influence on the signals of consecutive acetone exposure. The system might be used in the future for the monitoring of ambient air in work spaces.

Highly sensitive laser-based sensor for nanoparticles in air using a dual-ring-mirror setup.

One of the most frequently applied techniques to detect nanoparticles in air is analyzing laser light scattering. This technique is very flexible while offering high accuracy and reliability. Yet its functionality highly depends on the sensitivity of the measurement system components. Especially for miniaturized sensor devices with limited space, additional techniques are needed to preserve high intensity of scattered light. In our work we demonstrate a technique using two spherical ring mirrors to identify nanoparticles with diameters below 100 nm in a forward-scattering setup. We succeeded measuring polystyrene particles with diameters of 92 nm with a signal-to-noise-ratio of more than 10.

Cell-based sensor system using L6 cells for broad band continuous pollutant monitoring in aquatic environments.

Pollution of drinking water sources represents a continuously emerging problem in global environmental protection. Novel techniques for real-time monitoring of water quality, capable of the detection of unanticipated toxic and bioactive substances, are urgently needed. In this study, the applicability of a cell-based sensor system using selected eukaryotic cell lines for the detection of aquatic pollutants is shown. Readout parameters of the cells were the acidification (metabolism), oxygen consumption (respiration) and impedance (morphology) of the cells. A variety of potential cytotoxic classes of substances (heavy metals, pharmaceuticals, neurotoxins, waste water) was tested with monolayers of L6 cells (rat myoblasts). The cytotoxicity or cellular effects induced by inorganic ions (Ni(2+) and Cu(2+)) can be detected with the metabolic parameters acidification and respiration down to 0.5 mg/L, whereas the detection limit for other substances like nicotine and acetaminophen are rather high, in the range of 0.1 mg/L and 100 mg/L. In a close to application model a real waste water sample shows detectable signals, indicating the existence of cytotoxic substances. The results support the paradigm change from single substance detection to the monitoring of overall toxicity.

Fractional exhaled nitric oxide measurement with a handheld device.

A sensing system for fractional exhaled nitric oxide (FeNO) measurement is presented, which is characterized by a compact setup and a cost potential to be made available for the patient at home. The sensing is based on the work function measurement of a phthalocyanine-type sensing material, which is shown to be sufficiently sensitive for NO(2) in the ppb range. The transducer used to measure the work function is a field effect transistor with a suspended gate electrode. Selectivity is given with respect to other breath components including typically metabolic by-products. The measurement system includes breath treatments in a simple setup, which essentially are dehumidification and a quantitative conversion of NO to NO(2) with a conversion rate of approx. 95%, using a disposable oxidation catalyst. The accomplishment of the correct exhalation maneuver and feeding of the suited portion of exhaled air to the sensor is provided by breath sampling means. The sensor is not gas consuming. This allows us to fill the measurement chamber once, instead of establishing a gas flow for the measurement. This feature simplifies the device architecture. In this paper, we report on sensor characteristics, system architecture and measurement with artificial breath-gas as well as with human breath with the device.

Low-level and ultralow-volume hollow waveguide based carbon monoxide sensor.

We demonstrate an ultralow sample volume optical carbon monoxide sensor with detection sensitivity of 180 parts in 10(9) (1σ at 1 Hz). The utilization of a 2.3 µm surface-emitting laser directly coupled to a 3 m hollow capillary fiber as the gas cell is proven to be a compact, sensitive, and cost-efficient gas sensing concept. By mechanical vibration of the fiber, an absorbance resolution of 10(-5) is achieved, which is comparable to single-reflective (double-pass) cells. An improvement of sensitivity over the conventional single-reflective cell is thus approximately linearly scaled with the enhancement of the optical path length, which is usually more than 1 order of magnitude.

Solid state gas sensor research in Germany - a status report.

This status report overviews activities of the German gas sensor research community. It highlights recent progress in the field of potentiometric, amperometric, conductometric, impedimetric, and field effect-based gas sensors. It is shown that besides step-by-step improvements of conventional principles, e.g. by the application of novel materials, novel principles turned out to enable new markets. In the field of mixed potential gas sensors, novel materials allow for selective detection of combustion exhaust components. The same goal can be reached by using zeolites for impedimetric gas sensors. Operando spectroscopy is a powerful tool to learn about the mechanisms in n-type and in p-type conductometric sensors and to design knowledge-based improved sensor devices. Novel deposition methods are applied to gain direct access to the material morphology as well as to obtain dense thick metal oxide films without high temperature steps. Since conductometric and impedimetric sensors have the disadvantage that a current has to pass the gas sensitive film, film morphology, electrode materials, and geometrical issues affect the sensor signal. Therefore, one tries to measure directly the Fermi level position either by measuring the gas-dependent Seebeck coefficient at high temperatures or at room temperature by applying a modified miniaturized Kelvin probe method, where surface adsorption-based work function changes drive the drain-source current of a field effect transistor.

Platform for a hydrocarbon exhaust gas sensor utilizing a pumping cell and a conductometric sensor.

Very often, high-temperature operated gas sensors are cross-sensitive to oxygen and/or they cannot be operated in oxygen-deficient (rich) atmospheres. For instance, some metal oxides like Ga(2)O(3) or doped SrTiO(3) are excellent materials for conductometric hydrocarbon detection in the rough atmosphere of automotive exhausts, but have to be operated preferably at a constant oxygen concentration. We propose a modular sensor platform that combines a conductometric two-sensor-setup with an electrochemical pumping cell made of YSZ to establish a constant oxygen concentration in the ambient of the conductometric sensor film. In this paper, the platform is introduced, the two-sensor-setup is integrated into this new design, and sensing performance is characterized. Such a platform can be used for other sensor principles as well.