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The electrochemical determination of chemical oxygen demand (COD) presents a promising alternative to the standard method, addressing concerns related to toxic chemicals, extended measurement time, and automation challenges. This review aims to comprehensively examine the current state of research and offer insights for future advancements. The discussion spans three key areas: working electrode materials (including Cu-based, carbon-based, Boron-Doped Diamond (BDD), and PbO2), electrochemical methods (amperometry, coulometry, and voltammetry), and measurement setups. Special emphasis is placed on exploring the dependencies of the amperometric method on organic compounds and discerning the distinct application scopes of various electrochemical methods. Future perspectives are outlined for each research aspect. The review also delves into the evaluation of developed methods, proposing measures for a more standardized and cohesive evaluation approach. Through these efforts, the review seeks to propel research towards the practical application of electrochemical COD determination.

This study investigated the effect of different synthesis parameters including pre- and post-hydrothermal treatment on the formation of a high-quality SSZ-13 membrane layer. The membranes were identified initially by the gas tightness test, then were characterized by single gas permeation measurements applying H2, He, CO2, N2, CH4, and SF6 at room temperature. The results showed how each parameter affects the performance of the membrane, including structural defects in the formed selective layer, CO2 permeance, and the ideal CO2/CH4 permselectivity. This work focused on optimizing these parameters. An ideal CO2/CH4 permselectivity of up to 122 with CO2 permeance of ~3.72 × 10−6 [mol/(m2sPa)] and CO2/CH4 selectivity of 111 with CO2 permeance of 8.5 × 10−7 [mol/(m2sPa)] in an equimolar mixture at room temperature and pressure drop of 0.15 MPa was achieved. This is one of the highest performances compared to other publications for SSZ-13 or all-Si membranes.

Copper ores and concentrates thereof feature an increasingly notable content of impurities such as arsenic and other hazardous elements. As an alternative to the state-of-the-art partial roasting process, arsenic could be removed by the alkaline sulfide leaching of the copper concentrates. In order to optimize and understand the processes, knowledge of the speciation and oxidation states is essential. In addition to methods such as UV/Vis spectroscopy, chromatography and ICP/MS methods, 75As NMR spectroscopy may be useful for the differentiation and quantification of the various species. Although arsenate(V) has been characterized by 75As NMR some time ago, to our knowledge, there are no data on tetrathioarsenate(V) AsS43− and the mixed oxygen/sulfur substituted mono-, di- and trithioarsenates(V) AsOxS4−x3−, x = 3, 2, 1, respectively. Therefore, we investigated several model solutions and samples from Cu-As leaching with 75As NMR. The strongly alkaline conditions of the leaching solution proved to be very advantageous for that purpose. Both the tetrathioarsenate(V) and the mixed species AsOxS4−x3− (x = 1–3) could be characterized and provide valuable data for the quantification of the material flows in the leaching process.

Polymer–semiconductor hybrid materials or composites have been investigated with respect to their microstructure, optical, photoconductive, and ferroelectric properties. For this purpose, either CdSe quantum dots or (Cd:Zn)S microparticles were dispersed in poly(vinylidenefluoride-trifluoroethylene) solution and hot pressed to films. In both material systems, the electrical conductivity and the polarization behavior could be controlled by the intensity of the optical excitation. The simultaneous high optical transparency of the CdSe quantum-dot-based hybrid materials makes them particularly interesting for applications in the field of flexible, high-resolution sensors.

Part I of this series of papers focuses on plant and reactor engineering aspects of the TSL reactor technology. A general flowsheet is presented, while emphasis is given to the definition of different reactor zones in terms of fluid dynamics and occurring reactions. Then, the technical advantages of TSL processing, such as feed flexibility and high conversion rates (due to induced turbulence), low dust generation, and low fugitive emissions, are explained. In addition, the reactor is analyzed part by part, also taking into account patent literature, focusing on furnace design, settling furnaces for molten phase disengagement, feeding systems regarding input material streams such as concentrates and fuels, vessel cooling arrangements, off-gas system, and aspects associated with the refractory lining. Furthermore, specific focus is given to the centerpiece of the TSL reactor, i.e., the reactor lance. Associated developments have focused on establishing a slag coating to hinder lance wear, i.e., the development of cooling mechanisms (e.g., use of fluid-cooled lance and shroud arrangements), the increment of O2 enrichment within the incoming air stream, and influencing of fluid dynamics (e.g., O2 conversion at the lance tip, bubble formation, and bath splashing). Finally, comprehensive tables concerning process developments and commissioned TSL plants are provided thus concluding Part I of the review.

In Part II of this series of review papers, the reaction mechanisms, thermodynamics, slag chemistry and process flowsheets are analyzed concerning cases where the TSL bath smelter has found its application. These include the primary and secondary production routes of five non-ferrous metals (tin, copper, lead, nickel, zinc), ironmaking and two waste-processing applications (spent pot lining and municipal solid waste/related ash treatment). Thereby, chemistry and processing aspects of these processes are concisely reviewed here, allowing for clear and in-depth overview of related aspects. In contrast to Part I, the focus lies on a holistic analysis of the metallurgical processes themselves, especially the particularities induced by carrying them out in a TSL reactor rather than on the respective equipment and auxiliaries. The methodology employed per metal/application is presented briefly. Firstly, the feed type and associated statistical information are introduced, along with relevant process goals, e.g., the secondary metallurgy of copper involves the recovery of platinum group metals (PGMs) from waste from electrical and electronic equipment (WEEE). Subsequently, associated chemistry is discussed, including respective chemical equations, analysis of the reaction mechanisms and phase diagrams (especially of associated slag systems); these are redrawn using FactSage 8.1 (databases used: FactPS, FToxid, FTmisc, FTsalt and FTOxCN) and validated by comparing them with the literature. Then, based on the above understanding of chemistry and thermodynamics, the flowsheets of several industrial TSL plants are introduced and discussed while providing key figures associated with process conditions and input/output streams. Finally, this article culminates by providing a concise overview of the simulation and digitization efforts on TSL technology. In light of the foregoing discourse, this paper encapsulates basic principles and operational details, specifically those pertaining to TSL bath smelting operations within the non-ferrous industry, thereby offering valuable insights intended to benefit both scholarly researchers and industry professionals.

The increasing quantity and variety of organic contaminants discharged into surface and groundwater increase the necessity of additional and suitable water treatment methods, which can be incorporated into existing wastewater treatment plants. The huge variety of micropollutants and local variability of the composition of the organic load or matrix effects paired with multiple possible degradation processes lead to the requirement of a recommendation tool for the best possible water treatment method under given local conditions. Due to the diversity of physicochemical properties of micropollutants, such predictions are challenging. In this study, a quantitative correlation between the structural properties of certain micropollutants and their degradability using high-frequency sonolysis has been investigated. Therefore, Quantitative Structure-Property Relationship (QSPR) has been applied on a set of phenol derivates. To obtain the kinetic data, all experiments have been conducted in standardized, constant conditions for all 32 investigated phenol derivates. QSPR modelling was then executed using the software PaDEL for descriptor calculation and the software QSARINS for the overall modelling process including genetic algorithm (GA) and multiple linear regression (MLR). The final model consisting of 5 molecular descriptors was selected using a multi-criteria decision-making method based on extensive statistical parameters. The predictive power and robustness of the model was evaluated by means of internal cross validation and external validation using an independent validation set. The final selected model showed very good values for regression abilities, predictive power as well as stability (R2adj = 0.9455, CCCtr = 0.9777, Q2loo = 0.9285, CCCext = 0.9797 and Q2ext-F1 = 0.9711). The applicability domain of the QSPR model was defined based on the Williams plot and Insubria plot. The five OECD principles for the application of QSPR/QSAR modelling in industry and regulation were fulfilled in the whole process to the best of our knowledge, including the collection of the underlying experimental data as well as the entire modelling process. The final QSPR model included the molecular polarity and occurrence of hydrogen bonds as major influences on the reaction rate constants in accordance with previous studies. Nevertheless, potential biases in the selection of these descriptors due to the small size of the dataset were highlighted.

In this study, the effect of synthesis method on the structural stability of low-silica CHA zeolite crystals were investigated. For this purpose, template-free CHA crystals with similar chemical compositions were synthesized using seeded secondary growth and inter-zeolite transformation approaches. The stability performance of as-synthesized crystals was studied at temperatures, steam flow in a closed system, and acidic media. The results were analyzed using XRD, FTIR, DLS and FESEM. It was found both methods have similar structural stability behavior. The thermal stability investigation proved they have maintained their crystalline structure against heating, up to 800 °C, and at higher temperatures, the amorphous phase prevailed. The CHA crystals synthesized via both methods are stable in terms of hydrothermal stability up to 200 °C. Moreover, the results of chemical resistance showed CHA crystals exhibit excellent resistance to weak acidic medium, but against stronger acids, it has completely lost its crystallinity after 72 h.

Sodium-beta alumina is a solid-state electrolyte with outstanding chemical, electrochemical, and mechanical properties. Sodium polyaluminate is successfully employed in established Na–S and Na–NiCl2 cell systems. It is a promising candidate for all-solid-state sodium batteries. However, humidity affects the performance of this solid electrolyte. In this work, the effect of humidity on disk-shaped samples of Li-stabilized sodium-beta alumina stored in three different environments is quantified. We used impedance analysis and additional characterizations to investigate the consequences of the occurring degradation, namely ion exchange and subsequent buildup of surface layers. Sodium-beta alumina’s ionic conductivity gradually deteriorates up to two orders of magnitude. This is due to layers developed superficially during storage, while its fracture strength of 240 MPa remains unaffected. Changes in microstructure, composition, and cycle life of Na|BASE|Na cells highlight the importance of proper storage conditions: In just one week of improper storage, the critical current density collapsed from the maximum of 9.1 mA cm−2, one of the highest values reported for sodium-beta alumina, to 1.7 mA cm−2 at 25 °C. The results validate former observations regarding sodium-beta alumina’s moisture sensitivity and suggest how to handle sodium-beta alumina used in electrochemical cell systems.

Advanced oxidation processes are promising techniques for water remediation and degradation of micropollutants in aqueous systems. Since single processes such as sonolysis and photocatalysis exhibit limitations, combined AOP systems can enhance degradation efficiency. The present work addresses the synergistic intensification potential of an ultrasound-assisted photocatalysis (sonophotocatalysis) for bisphenol A degradation with a low-frequency sonotrode (f = 20 kHz) in a batch-system. The effects of energy input and suspended photocatalyst dosage (TiO2-nanoparticle, m = 0–0.5 g/L) were investigated. To understand the synergistic effects, the sonication characteristics were investigated by bubble-field analysis, hydrophone measurements, and chemiluminescence of luminol to identify cavitation areas due to the generation of hydroxyl radicals. Comparing the sonophotocatalysis with sonolysis and photocatalysis (incl. mechanical stirring), synergies up to 295% and degradation rates of up to 1.35 min−1 were achieved. Besides the proof of synergistic intensification, the investigation of energy efficiency for a degradation degree of 80% shows that a process optimization can be realized. Thus, it could be demonstrated that there is an effective limit of energy input depending on the TiO2 dosage.

The recycling of material containing precious metals can lead to the entry of ruthenium into the copper electrowinning process, by so far unknown effects. There, ruthenium is oxidized to highly volatile ruthenium tetroxide. In order to avoid ruthenium losses during electrolysis, the oxidation behavior of ruthenium in copper electrowinning was investigated by testing different oxygen overvoltages using lead alloy and diamond anodes. Furthermore, the temperature and the current density were varied to investigate a possible chemical or electrochemical reaction. The results of the study show that ruthenium is not directly electrochemically oxidized to ruthenium tetroxide at the anode. Especially at anodes with high oxygen overvoltage, the formation of other oxidants occurs parallel to the oxygen evolution in the electrolyte. These oxidants oxidize ruthenium compounds to highly volatile ruthenium tetroxide by chemical reactions. These reactions depend mainly on temperature; the formation of the active oxidants depends on the anodic potential. To avoid ruthenium losses in the copper electrowinning process, anodes with a low anodic potential should be used at low electrolyte temperatures.

The rapid development of light-emitting-diode (LED) technology is attributed to its superiority over light sources of earlier generations. Although LED lamps, compared to compact fluorescent lamps, are considered less harmful to the environment, there is still no efficient solution to deal with them at the end of their lifecycle. The first part of the study provides a detailed characterisation of LED lamps, focusing on their most interesting component: the LED module. LED packages attached to the module are highly enriched with Ga, In, Pd, Ag, Au, Sr, Y, Ce, Eu, Gd, and Lu, with the content of each element varying greatly depending on the LED technology. In the second part of this research, two new approaches for liberation and concentration of valuable components from LED modules are presented and compared: a chemical route and a thermal route. The chemical treatment leads to a highly selective separation of LED chips and encapsulation. Enrichment factors up to about 125 are achieved, and a concentrate is obtained containing approximately 14 wt% of the aforementioned valuable components. However, the process requires aromatic solvents, which are viewed as toxic. The thermal treatment results in separation of the aluminium heat sink from all other components of the LED module. Enrichment is approximately ten times lower, but the approach is technically feasible.

Pyrocatalysis uses thermally excited pyroelectric materials for the generation of reactive oxygen species in water. This unique feature allows it to harvest energy in the form of natural temperature gradients or waste heat from industrial processes in order to degrade organic pollutants at low costs. Its further development into an advanced oxidation process for water remediation is dependent on the availability of pH-robust and nonspecific redox assays for the determination of its oxidation capability. Nevertheless, previous studies neglected the influence of pH changes and they were focused mainly on the degradation of one organic compound or specific chemical dosimetries. In this study, a pH-robust and nonspecific reaction protocol of the dichlorofluorescein assay was established for the investigation of the oxidation capability of the pyrocatalytic process. This reaction protocol was tested on three pyroelectric powders (LiNbO3, LiTaO3, BaTiO3) in different amounts and it overcomes major constraints of a previously used dichlorodihydrofluorescein diacetate-based reaction protocol. Instead of its diacetate, dichlorodihydrofluorescein was used as fluorogenic probe and its concentration was drastically reduced to 1 μM. For the first time, these changes enable the determination and comparison of the oxidation capability independently of pH-rising processes, which are present for all investigated pyroelectric powders up to a pH of 11. Additionally, the precision of the dichlorofluorescein assay was drastically increased and the determination and consideration of autoxidation processes was enabled. Of all three pyroelectric powders, BaTiO3 exhibited the highest oxidation capability with a linear increase with respect to the powder amount.

The state-of-the-art technology of raw silver refining in a silver nitrate-based electrorefining process (Moebius-electrolysis) is accompanied by several disadvantages, both from a technological and from an ecological point of view. In addition, increasing concentrations of critical impurities from secondary sources, like palladium, in raw silver are a further challenge for the future of silver refining. Thus, there is strong motivation for the development of an adequate, alternative process of raw silver refining to substitute the existing Moebius-electrolysis. Due to its less environmentally toxic character and the high aqueous solubility of its silver salt, methanesulfonic acid (MSA) is a possible base chemical for the design of an efficient refining method based on leaching of raw silver followed by electrowinning, with less ecological and technological complications. In this paper the results of some fundamental investigations on the leaching of raw silver granules, containing approx. 94% silver, with methanesulfonic acid and hydrogen peroxide as an oxidation agent are presented. Agitation leaching experiments were conducted on a laboratory scale and the effects of the solid concentration, the hydrogen peroxide dosage and the temperature as leaching parameters were studied. The obtained results indicate that silver leaching yields of more than 90% are achievable with leaching at elevated temperatures of 65 °C or 80 °C, solid concentrations of 500 g/L and at a stoichiometric H2O2:Ag-ratio of 3:1. Increased solid concentrations greater than 500 g/L and elevated temperatures of 65 °C or 80 °C additionally improved the selectivity of the process regarding the leaching of Pd.

Na-β″-alumina is the commercially most successful solid electrolyte due to its application in ZEBRA and NAS® batteries. In this work, Li-stabilized Na-β″-alumina electrolytes were doped with 3d transition metal oxides, namely TiO2, Mn3O4, and NiO, in order to improve their ionic conductivity and fracture strength. Due to XRD and EDX measurements, it was concluded that Mn- and Ni-ions are incorporated into the crystal lattice of Na-β″-alumina. In contrast, TiO2 doping results in the formation of secondary phases that enable liquid-assisted sintering at temperatures as low as 1500 °C. All dopants increased the characteristic fracture strength of the electrolytes; 1.5 wt% of NiO doping proved to be most efficient and led to a maximal characteristic fracture strength of 296 MPa. Regarding the ionic conductivity, TiO2 doping showed the uppermost value of up to 0.30 S cm−1 at 300 °C. In contrast to the other dopants, TiO2 doping lowered the sintering temperature needed to obtain a dense, stable, and highly conductive Na-β″-alumina electrolyte suitable for applications in Na based batteries.

A new preparation concept of a partially porous solid-state bilayer electrolyte (BE) for high-temperature sodium-ion batteries has been developed. The porous layer provides mechanical strength and is infiltrated with liquid and highly conductive NaAlCl4 salt, while the dense layer prevents short circuits. Both layers consist, at least partially, of Na-β-alumina. The BEs are synthesized by a three-step procedure, including a sol-gel synthesis, the preparation of porous, calcined bulk material, and spin coating to deposit a dense layer. A detailed study is carried out to investigate the effect of polyethylene oxide (PEO) concentration on pore size and crystallization of the bulk material. The microstructure and crystallographic composition are verified for all steps via mercury intrusion, X-ray diffraction, and scanning electron microscopy. The porous bulk material exhibits an unprecedented open porosity for a NaxAlOy bilayer-system of ≤57% with a pore size of ≈200–300 nm and pore volume of ≤0.3 cm3∙g−1. It contains high shares of crystalline α-Al2O3 and Na-β-alumina. The BEs are characterized by impedance spectroscopy, which proved an increase of ionic conductivity with increasing porosity and increasing Na-β-alumina phase content in the bulk material. Ion conductivity of up to 0.10 S∙cm−1 at 300 °C is achieved.

The wetting behavior was measured for Al2O3-C in contact with AlSi7Mg with a conventional sessile drop test (vacuum, 950 °C and 180 min) and a sessile drop test with a capillary purification unit (vacuum, 730 °C and 30 min). The conventional test yielded contact angles of around 92°, whereas the sessile drop measurement with capillary purification showed a strongly non-wetting behavior with a determined apparent contact angle of the rolling drop of 157°. Filtration tests, which were repeated twice, showed that the Al2O3-C filter possessed a better filtration behavior than the Al2O3 reference filter. For both filtration trials, the PoDFA (porous disc filtration analysis) index of the Al2O3-C filter sample was equal to half of the PoDFA index of the Al2O3 reference filter sample, indicating a significantly improved filtration performance when using Al2O3-C filter. Notable is the observation of a newly formed layer between the aluminum and the Al2O3-C coating. The layer possessed a thickness between 10 µm up to 50 µm and consisted of Al, C, and O, however, with different ratios than the original Al2O3-C coating. Thermodynamic calculations based on parameters of the wetting and filtration trials underline the possible formation of an Al4O4C-layer.