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Potassium–oxygen batteries (KOBs) are a promising energy storage technology with high theoretical energy density, low overpotential and a long cycle life. The cathode microstructure plays a significant role in the electrochemical performance of KOB. In this article, hierarchical porosity was introduced to commercially available carbon paper cathodes by thermal pretreatment in air at different pretreatment times. This pretreatment modifies the properties, such as surface area, defects, oxygen functional groups, etc. The discharge performance was determined at three different current densities, i.e., 0.1 mA/cm2, 0.5 mA/cm2, and 1.0 mA/cm2. It has been found that an increase in specific surface area with the introduction of micropores and mesopores is beneficial for the improvement in the discharge capacity by enabling homogeneous discharge product, KO2 distribution and high degrees of pore filling over the volume of the cathode. A reduction in the discharge overpotentials was observed, which is attributed to the introduction of oxygenic functional groups and defects. Samples treated for the longest pretreatment time of 24 h showed the highest discharge capacity of 5 mAh/cm2 and lowest discharge overpotential of 0.03 V. [ABSTRACT FROM AUTHOR]

Future vehicle powertrain systems with internal combustion engines must achieve higher efficiencies and further reduced pollutant emissions. This will require the application of new advanced technologies. Against this background, this paper presents a holistic approach to reduce temporally the wall heat losses, and hydrocarbon and carbon monoxide emissions with thermal coatings on the combustion chamber walls. For this purpose, an yttria-stabilized zirconia (YSZ) coating is applied and evaluated by different methods. The thin layer in combination with the low thermal effusivity of the material allows the wall temperature to follow the gas temperature and perform a so-called thermal swing. The interaction between an uncoated and a YSZ-coated wall with the flame front as well as partially burned gas was investigated. First, in terms of the coating's potential to reduce the flame quenching distance using an optical method in a constant volume combustion chamber. Second, regarding its influence on the near-wall gas composition, which was analyzed with in-situ diffuse reflectance infrared Fourier transform spectroscopy measurements and a fast gas sampling technique on a single-cylinder engine. From this, it could be derived that the quenching distance can be reduced by 10% at ambient conditions and by 5% at an elevated temperature of 200 °C by using the coating. These findings also support the results that have been obtained by the near-wall gas composition measurements, where a reduced total hydrocarbon emission was found with the applied coating. [ABSTRACT FROM AUTHOR]

Melphalan (Mel) is an antineoplastic widely used in cancer and other diseases. Its low solubility, rapid hydrolysis, and non-specificity limit its therapeutic performance. To overcome these disadvantages, Mel was included in β-cyclodextrin (βCD), which is a macromolecule that increases its aqueous solubility and stability, among other properties. Additionally, the βCD–Mel complex has been used as a substrate to deposit silver nanoparticles (AgNPs) through magnetron sputtering, forming the βCD–Mel–AgNPs crystalline system. Different techniques showed that the complex (stoichiometric ratio 1:1) has a loading capacity of 27%, an association constant of 625 M−1, and a degree of solubilization of 0.034. Added to this, Mel is partially included, exposing the NH2 and COOH groups that stabilize AgNPs in the solid state, with an average size of 15 ± 3 nm. Its dissolution results in a colloidal solution of AgNPs covered by multiple layers of the βCD–Mel complex, with a hydrodynamic diameter of 116 nm, a PDI of 0.4, and a surface charge of 19 mV. The in vitro permeability assays show that the effective permeability of Mel increased using βCD and AgNPs. This novel nanosystem based on βCD and AgNPs is a promising candidate as a Mel nanocarrier for cancer therapy. [ABSTRACT FROM AUTHOR]

Dacarbazine (DB) is an antineoplastic drug extensively used in cancer therapy. However, present limitations on its performance are related to its low solubility, instability, and non-specificity. To overcome these drawbacks, DB was included in β-cyclodextrin (βCD), which increased its aqueous solubility and stability. This new βCD@DB complex has been associated with plasmonic gold nanoparticles (AuNPs), and polyethylene glycol (PEG) has been added in the process to increase the colloidal stability and biocompatibility. Different techniques revealed that DB allows for a dynamic inclusion into βCD, with an association constant of 80 M−1 and a degree of solubilization of 0.023, where βCD showed a loading capacity of 16%. The partial exposure of the NH2 group in the included DB allows its interaction with AuNPs, with a loading efficiency of 99%. The PEG-AuNPs-βCD@DB nanosystem exhibits an optical plasmonic absorption at 525 nm, a surface charge of −29 mV, and an average size of 12 nm. Finally, laser irradiation assays showed that DB can be released from this platform in a controlled manner over time, reaching a concentration of 56 μg/mL (43% of the initially loaded amount), which, added to the previous data, validates its potential for drug delivery applications. Therefore, the novel nanosystem based on βCD, AuNPs, and PEG is a promising candidate as a new nanocarrier for DB. [ABSTRACT FROM AUTHOR]

The efficiency and robustness of selective catalytic reduction (SCR) by NH3 catalysts for exhaust gas purification, especially of heavy-duty diesel engines, will continue to play a major role, despite the increasing electrification of powertrains. With that in mind, the effect of the synthesis scale on commercially available Cu-exchanged chabazite catalysts for SCR was investigated through physicochemical characterizations and catalytic tests. During hydrothermal aging, both industrial and lab-scale prepared catalysts underwent structural dealumination of the zeolite framework and redistribution of the Al sites. Although both catalysts demonstrated similar NO conversion activity under SCR conditions, the lab-scale catalyst showed higher selectivity and lower activity in NH3 oxidation. Variations in N2O formation and NH3 oxidation rate were found to correlate with the formation of different copper species, and the compositions become less controllable in industrial-scale process. This case study focused on routes of ion exchange, and the results provide new insights into catalytic performance of the industrially-produced zeolites. [ABSTRACT FROM AUTHOR]

We introduce a microwave (MW)-assisted heterogeneous catalytical setup, which we carefully examined for its thermal and performance characteristics. Although MW-assisted heterogeneous catalysis has been widely explored in the past, there is still need for attention towards the specific experimental details, which may complicate the interpretation of results and comparability in general. In this study we discuss technical and material related factors influencing the obtained data from MW-assisted heterogeneous catalysis, specifically in regards to the oxidation of carbon monoxide over a selected perovskite catalyst, which shall serve as a model reaction for exhaust gas aftertreatment. A high degree of comparability between different experiments, both in terms of setup and the catalysts, is necessary to draw conclusions regarding this promising technology. Despite significant interest from both fundamental and applied research, many questions and controversies still remain and are discussed in this study. A series of deciding parameters is presented and the influence on the data is discussed. To control these parameters is both a challenge but also an opportunity to gain advanced insight into MW-assisted catalysis and to develop new materials and processes. The results and discussion are based upon experiments conducted in a monomode MW-assisted catalysis system employing powdered solid-state perovskite oxides in a fixed bed reactor. The discussion covers critical aspects concerning the determination of the actual catalyst temperature, the homogeneity of the thermal distribution, time, and local temperature relaxation (i.e., thermal runaway effects and hotspot formation), particle size effects, gas flow considerations, and system design. [ABSTRACT FROM AUTHOR]

Lithium-oxygen (Li-O2) batteries require scalable air electrode concepts and a sensible choice of operation parameters to achieve their promised energy densities. Furthermore, different test parameters are often investigated individually, but rarely brought together in order to optimize the discharge process and unlock the full discharge capability of an air electrode. In this work, we present a highly porous electrode based on graphite nanosheets (GNS) and discuss the impact of the discharge current density and the oxygen pressure as battery test parameters, as well as the electrolyte salt and volume, on the discharge behavior. In particular, changing the electrolyte salt from LiNO3 to LiTFSI proved to be an important step towards better cell performance, because synergistic effects of the electrolyte and GNS greatly enhance the carbon-specific capacity. The optimized combination of the aforementioned parameters enabled a remarkably high discharge capacity of 56.3 mAh/cm² (5860 mAh/gcarbon) obtained at 150 μA/cm² (15.6 mA/gcarbon), resulting in the almost complete conversion of the lithium anode. These experimental results are an important step towards practical high-capacity air electrodes for Li-O2 batteries. [ABSTRACT FROM AUTHOR]

Surface acoustic wave (SAW) devices are well known for mass-sensitive sensor applications. In biosensing applications, chemical and biochemically evoked binding processes on surfaces are detected in liquid environments using delay line or resonator sensor configurations, preferably in combination with the appropriate microfluidic devices. All configurations share the common feature of analyzing the transmission characteristic of the propagating SAW. In this paper, a novel SAW-based impedance sensor type is introduced which uses only one interdigital transducer (IDT), simultaneously as the SAW generator and the sensor element. Here, the input port reflection coefficient S11 is measured at the IDT instead of the commonly used S21 transmission forward gain parameter. Thus, a sharp and distinct peak of the S11 spectrum is obtained, enabling a comfortable direct readout of the sensor signal. Proof of the concept was gained by analyzing the specific binding of the 4-mercaptophenylacetic acid gold nanoparticles (MPA-AuNP) directly to the IDT surface. The corresponding binding kinetic of the MPA-AuNP on the functionalized gold surface has been analyzed and a sensitivity of 7.4 mW nM-1 has been determined. [ABSTRACT FROM AUTHOR]

Proton transport is an elementary process in the selective catalytic reduction of nitrogen oxides by ammonia (DeNOx by NH3-SCR) using metal-exchanged zeolites as catalysts. This review summarizes recent advancements in the study of proton transport in zeolite catalysts using in situ electrical impedance spectroscopy (IS) under NH3-SCR reaction conditions. Different factors, such as the metal cation type, metal exchange level, zeolite framework type, or formation of intermediates, were found to influence the proton transport properties of zeolite NH3-SCR catalysts. A combination of IS with diffuse reflection infrared Fourier transformation spectroscopy in situ (in situ IS-DRIFTS) allowed to achieve a molecular understanding of the proton transport processes. Several mechanistic aspects, such as the NH3-zeolite interaction, NO-zeolite interaction in the presence of adsorbed NH3, or formation of NH4+ intermediates, have been revealed. These achievements indicate that IS-based in situ methods as complementary tools for conventional techniques (e.g., in situ X-ray absorption spectroscopy) are able to provide new perspectives for the understanding of NH3-SCR on zeolite catalysts. [ABSTRACT FROM AUTHOR]

Zeolites have been found to be promising sensor materials for a variety of gas molecules such as NH3, NOx, hydrocarbons, etc. The sensing effect results from the interaction of the adsorbed gas molecules with mobile cations, which are non-covalently bound to the zeolite lattice. The mobility of the cations can be accessed by electrical low-frequency (LF; mHz to MHz) and high-frequency (HF; GHz) impedance measurements. Recent developments allow in situ monitoring of catalytic reactions on proton-conducting zeolites used as catalysts. The combination of such in situ impedance measurements with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), which was applied to monitor the selective catalytic reduction of nitrogen oxides (DeNOx-SCR), not only improves our understanding of the sensing properties of zeolite catalysts from integral electric signal to molecular processes, but also bridges the length scales being studied, from centimeters to nanometers. In this work, recent developments of zeolite-based, impedimetric sensors for automotive exhaust gases, in particular NH3, are summarized. The electrical response to NH3 obtained from LF impedance measurements will be compared with that from HF impedance measurements, and correlated with the infrared spectroscopic characteristics obtained from the DRIFTS studies of molecules involved in the catalytic conversion. The future perspectives, which arise from the combination of these methods, will be discussed. [ABSTRACT FROM AUTHOR]

Over the past 20 years, 68Ga-labelled radiopharmaceuticals have become an important part in clinical routine. However, the worldwide supply with 68Ge/68Ga generators is limited as well as the number of patient doses per batch of 68Ga radiopharmaceutical. In the recent years, a new technique appeared, making use of the ease of aqueous labelling via chelators as with 68Ga but using 18F instead. This technique takes advantage of the strong coordinative bond between aluminium and fluoride, realized in the aqueous cation [Al18F]2+. Most applications to date make use of one-pot syntheses with free Al(III) ions in the system. In contrast, we investigated the labelling approach split into two steps: generating the Al-bearing precursor in pure form and using this Al compound as a precursor in the labelling step with aqueous [18F]fluoride. Hence, no free Al3+ ions are present in the labelling step. We investigated the impact of parameters: temperature, pH, addition of organic solvent, and reaction time using the model chelator NH2-MPAA-NODA. With optimized parameters we could stably achieve a 80% radiochemical yield exerting a 30-min reaction time at 100 °C. This technique has the potential to become an important approach in radiopharmaceutical syntheses. [ABSTRACT FROM AUTHOR]

The AnyBody Modeling System™ (AMS) is a musculoskeletal software simulation solution using inverse dynamics analysis. It enables the determination of muscle and joint forces for a given bodily motion. The recording of the individual movement and the transfer into the AMS is a complex and protracted process. Researches indicated that the contactless, visual Leap Motion Controller (LMC) provides clinically meaningful motion data for hand tracking. Therefore, the aim of this study was to integrate the LMC hand motion data into the AMS in order to improve the process of recording a hand movement. A Python-based interface between the LMC and the AMS, termed ROSE Motion, was developed. This solution records and saves the data of the movement as Biovision Hierarchy (BVH) data and AnyScript vector files that are imported into the AMS simulation. Setting simulation parameters, initiating the calculation automatically, and fetching results is implemented by using the AnyPyTools library from AnyBody. The proposed tool offers a rapid and easy-to-use recording solution for elbow, hand, and finger movements. Features include animation, cutting/editing, exporting the motion, and remote controlling the AMS for the analysis and presentation of musculoskeletal simulation results. Comparing the motion tracking results with previous studies, covering problems when using the LMC limit the correctness of the motion data. However, fast experimental setup and intuitive and rapid motion data editing strengthen the use of marker less systems as the herein presented compared to marker based motion capturing. [ABSTRACT FROM AUTHOR]

Dynamic motion of NH3-solvated Cu sites in Cu-chabazite (Cu-CHA) zeolites, which are the most promising and state-of-the-art catalysts for ammonia-assisted selective reduction of NOx (NH3-SCR) in the aftertreatment of diesel exhausts, represents a unique phenomenon linking heterogeneous and homogeneous catalysis. This review first summarizes recent advances in the theoretical understanding of such low-temperature Cu dynamics. Specifically, evidence of both intra-cage and inter-cage Cu motions, given by ab initio molecular dynamics (AIMD) or metadynamics simulations, will be highlighted. Then, we will show how, among others, synchrotron-based X-ray spectroscopy, vibrational and optical spectroscopy (diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) and diffuse reflection ultraviolet-visible spectroscopy (DRUVS)), electron paramagnetic spectroscopy (EPR), and impedance spectroscopy (IS) can be combined and complement each other to follow the evolution of coordinative environment and the local structure of Cu centers during low-temperature NH3-SCR reactions. Furthermore, the essential role of Cu dynamics in the tuning of low-temperature Cu redox, in the preparation of highly dispersed Cu-CHA catalysts by solid-state ion exchange method, and in the direct monitoring of NH3 storage and conversion will be presented. Based on the achieved mechanistic insights, we will discuss briefly the new perspectives in manipulating Cu dynamics to improve low-temperature NH3-SCR efficiency as well as in the understanding of other important reactions, such as selective methane-to-methanol oxidation and ethene dimerization, catalyzed by metal ion-exchanged zeolites. [ABSTRACT FROM AUTHOR]

Lithium-oxygen (Li-O2) batteries require rational air electrode concepts to achieve high energy densities. We report a simple but effective electrode design based on graphite nanosheets (GNS) as active material to facilitate the discharge reaction. In contrast to other carbon forms we tested, GNS show a distinctive two-step discharge behavior. Fundamental aspects of the battery's discharge profile were examined in different depths of discharge using scanning electron microscopy and electrochemical impedance spectroscopy. We attribute the second stage of discharge to the electrochemically induced expansion of graphite, which allows an increase in the discharge product uptake. Raman spectroscopy and powder X-ray diffraction confirmed the main discharge product to be Li2O2, which was found as particulate coating on GNS at the electrode top, and in damaged areas at the bottom together with Li2CO3 and Li2O. Large discharge capacity comes at a price: the chemical and structural integrity of the cathode suffers from graphite expansion and unwanted byproducts. In addition to the known instability of the electrode–electrolyte interface, new challenges emerge from high depths of discharge. The mechanistic origin of the observed effects, as well as air electrode design strategies to deal with them, are discussed in this study. [ABSTRACT FROM AUTHOR]

LiNi0.5Mn1.5O4 (LNMO) spinel has been extensively investigated as one of the most promising high-voltage cathode candidates for lithium-ion batteries. The electrochemical performance of LNMO, especially its rate performance, seems to be governed by its crystallographic structure, which is strongly influenced by the preparation methods. Conventionally, LNMO materials are prepared via solid-state reactions, which typically lead to microscaled particles with only limited control over the particle size and morphology. In this work, we prepared Ni-doped LiMn2O4 (LMO) spinel via the polyol method. The cycling stability and rate capability of the synthesized material are found to be comparable to the ones reported in literature. Furthermore, its electronic charge transport properties were investigated by local electrical transport measurements on individual particles by means of a nanorobotics setup in a scanning electron microscope, as well as by performing DFT calculations. We found that the scarcity of Mn3+ in the LNMO leads to a significant decrease in electronic conductivity as compared to undoped LMO, which had no obvious effect on the rate capability of the two materials. Our results suggest that the rate capability of LNMO and LMO materials is not limited by the electronic conductivity of the fully lithiated materials. [ABSTRACT FROM AUTHOR]

The mobility of NH3-solvated Cu ions within the zeolite framework has been recently identified as a key factor for the kinetics of the selective catalytic reduction of NOx with NH3 (NH3-SCR) over Cu-zeolite catalysts at low temperatures. Here, we utilize in situ impedance spectroscopy to explore the mobility of NH3-solvated CuII ions, i.e., CuII(NH3)n, in Cu-SSZ-13 and Cu-ZSM-5 zeolites with varied Cu ion exchange levels, and observed that both the zeolite framework (CHA or MFI) and the Cu exchange level influence the high-frequency dielectric relaxation processes that are associated with the short-range (local) motion of CuII(NH3)n. Our results suggest that the local motion of CuII(NH3)n species is favored within the CHA framework due to the unique cage structure, and thereby contribute to the overall ion conductivity at high frequencies, which, on the contrary, is not observed for ZSM-5, where NH3-solvated Cu2+ ions do not experience a comparable constrained space for local motion. This study sheds new light on the mobility of Cu active sites under NH3-SCR related reaction conditions and may contribute to an advanced understanding of the underlying mechanism. [ABSTRACT FROM AUTHOR]

Lithium-oxygen (Li-O 2 ) batteries require rational air electrode concepts to achieve high energy densities. We report a simple but effective electrode design based on graphite nanosheets (GNS) as active material to facilitate the discharge reaction. In contrast to other carbon forms we tested, GNS show a distinctive two-step discharge behavior. Fundamental aspects of the battery's discharge profile were examined in different depths of discharge using scanning electron microscopy and electrochemical impedance spectroscopy. We attribute the second stage of discharge to the electrochemically induced expansion of graphite, which allows an increase in the discharge product uptake. Raman spectroscopy and powder X-ray diffraction confirmed the main discharge product to be Li 2 O 2 , which was found as particulate coating on GNS at the electrode top, and in damaged areas at the bottom together with Li 2 CO 3 and Li 2 O. Large discharge capacity comes at a price: the chemical and structural integrity of the cathode suffers from graphite expansion and unwanted byproducts. In addition to the known instability of the electrode-electrolyte interface, new challenges emerge from high depths of discharge. The mechanistic origin of the observed effects, as well as air electrode design strategies to deal with them, are discussed in this study.

Surface acoustic wave (SAW) devices are well known for mass-sensitive sensor applications. In biosensing applications, chemical and biochemically evoked binding processes on surfaces are detected in liquid environments using delay line or resonator sensor configurations, preferably in combination with the appropriate microfluidic devices. All configurations share the common feature of analyzing the transmission characteristic of the propagating SAW. In this paper, a novel SAW-based impedance sensor type is introduced which uses only one interdigital transducer (IDT), simultaneously as the SAW generator and the sensor element. Here, the input port reflection coefficient S 11 is measured at the IDT instead of the commonly used S 21 transmission forward gain parameter. Thus, a sharp and distinct peak of the S 11 spectrum is obtained, enabling a comfortable direct readout of the sensor signal. Proof of the concept was gained by analyzing the specific binding of the 4-mercaptophenylacetic acid gold nanoparticles (MPA-AuNP) directly to the IDT surface. The corresponding binding kinetic of the MPA-AuNP on the functionalized gold surface has been analyzed and a sensitivity of 7.4 mΩ nM -1 has been determined., Competing Interests: The authors declare no conflicts of interest.

Zeolites have been found to be promising sensor materials for a variety of gas molecules such as NH₃, NOx, hydrocarbons, etc. The sensing effect results from the interaction of the adsorbed gas molecules with mobile cations, which are non-covalently bound to the zeolite lattice. The mobility of the cations can be accessed by electrical low-frequency (LF; mHz to MHz) and high-frequency (HF; GHz) impedance measurements. Recent developments allow in situ monitoring of catalytic reactions on proton-conducting zeolites used as catalysts. The combination of such in situ impedance measurements with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), which was applied to monitor the selective catalytic reduction of nitrogen oxides (DeNOx-SCR), not only improves our understanding of the sensing properties of zeolite catalysts from integral electric signal to molecular processes, but also bridges the length scales being studied, from centimeters to nanometers. In this work, recent developments of zeolite-based, impedimetric sensors for automotive exhaust gases, in particular NH₃, are summarized. The electrical response to NH₃ obtained from LF impedance measurements will be compared with that from HF impedance measurements, and correlated with the infrared spectroscopic characteristics obtained from the DRIFTS studies of molecules involved in the catalytic conversion. The future perspectives, which arise from the combination of these methods, will be discussed.