Publikationen

The widespread contamination of water resources with emerging organic contaminants necessitates the development of sustainable and cost-effective water treatment technologies. Adsorption, as a widely used water remediation process, is hampered by severe performance limitations against ionic and hydrophilic organic contaminants. In addition, no facile on-site regeneration techniques are available. Electrosorption of organic compounds (EOC) is a promising alternative to not only improve adsorption performance, but also to facilitate adsorbent regeneration by green electricity. The number of studies on EOC has grown exponentially over the past decades. There are numerous examples showing that applied electric potentials can significantly enhance the adsorption affinity, capacity, and kinetics of conductive carbon adsorbents. However, whether these effects are specific to certain compound classes or more generally applicable remains unclear as well as the optimal criteria for designing EOC processes. Therefore, we critically evaluated the current state of the art of EOC in terms of active control of adsorption and desorption processes and the achievable effects for ionic and neutral organic compounds. Through a detailed consideration of compound speciation and surface chemistry of electrode materials, we derive mechanistic insights into the EOC process and discuss differences between electrosorption of inorganic and organic compounds. We provide definitions and propose insightful performance parameters to unify the rapidly growing EOC research. Potential application scenarios and future research directions are discussed. Overall, EOC is less likely to be a one-fits-all solution for removing contaminants, but adds a valuable tool especially for the hydrophilic and ionic organic contaminants that challenge conventional adsorption processes.

Ionic liquid mixtures show promise as electrolytes for supercapacitors with nanoporous electrodes. Herein, we investigate theoretically and with experiments how binary electrolytes comprising a common anion and two types of differently-sized cations affect capacitive energy storage. We find that such electrolytes can enhance the capacitance of single nanopores and nanoporous electrodes under potential differences negative relative to the potential of zero charge. For a two-electrode cell, however, they are beneficial only at low and intermediate cell voltages, while a neat ionic liquid performs better at higher voltages. We reveal subtle effects of how the distribution of pores accessible to different types of ions correlates with charge storage and suggest approaches to increase capacitance and stored energy density with ionic liquid mixtures.

Electrochemical desalination shows promise for ion-selective, energy-efficient water desalination. This work reviews performance metrics commonly used for electrochemical desalination. We provide a step-by-step guide on acquiring, processing, and calculating raw desalination data, emphasizing informative and reliable figures of merit. A typical experiment uses calibrated conductivity probes to relate measured conductivity to concentration. Using a standard electrochemical desalination cell with activated carbon electrodes, we demonstrate the calculation of desalination capacity, charge efficiency, energy consumption, and ion selectivity metrics. We address potential pitfalls in performance metric calculations, including leakage current (charge) considerations and aging of conductivity probes, which can lead to inaccurate results. The relationships between pH, temperature, and conductivity are explored, highlighting their influence on final concentrations. Finally, we provide a checklist for calculating performance metrics and planning electrochemical desalination tests to ensure accuracy and reliability. Additionally, we offer simplified spreadsheet tools to aid data processing, system design, estimations, and upscaling.

Electrochemically converting nitrate, widely distributed in industrial wastewater and contaminated water bodies, into ammonia is a promising route for resource recovery and wastewater treatment. Meanwhile, treating harmful algal blooms (HABs) is presented worldwide, are time and resource-consuming, and carries a high CO2 footprint. Rather than considering this carbon and nitrogen-rich biomass as disposable waste, consider it a vast renewable resource. Therefore, this study presents a Fe-dispersed carbon-based catalyst derived from HABs biomass, with a maximum ammonia yield rate of 16449 μg h−1 cm−2 (1.2 mmol h−1 mgcat−1) and NH3 Faradaic efficiency of 87.3%. This catalyst also possessed decent stability with continuous operation over 50 h. Experimental and theoretical calculation results reveal that the Fe-N4 site facilitates electrocatalytic nitrate reduction reaction by reducing the energy barriers of the NO3–to-NH3 pathway. Thus, this strategy of upcycling HABs biomass waste into functional catalysts offers a multipronged approach to renewable and carbon-neutral energy technologies.

Sodium ion insertion plays a critical role in developing robust sodium-ion technologies (batteries and hybrid supercapacitors). Diffusion coefficient values of sodium (DNa+) in tin phosphide between 0.1 V and 2.0 V vs. Na/Na+ are systematically determined by galvanostatic intermittent titration technique (GITT), electrochemical impedance spectroscopy (EIS), and potentiostatic intermittent titration technique (PITT). These values range between 4.55 × 10−12 cm2 s−1 and 1.94 × 10−8 cm2 s−1 and depend on the insertion/de-insertion current and the thickness of the electrode materials. Additionally, DNa+ values differ between the first and second cation insertion because of the solid electrolyte interface (SEI) formation. DNa+ vs. insertion potential alters non-linearly in a “W” form due to the strong interactions of Na+ with tin phosphide particles. The results reveal that GITT is a more appropriate electrochemical technique than PITT and EIS for evaluating DNa+ in tin phosphide.

Heavy metal pollution is a key environmental problem. Selectively extracting heavy metals could accomplish water purification and resource recycling simultaneously. Adsorption is a promising approach with a facile process, adaptability for the broad concentration of feed water, and high selectivity. However, the adsorption method faces challenges in synthesizing high-performance sorbents and regenerating adsorbents effectively. FeOOH is an environmentally friendly sorbent with low-cost production on a large scale. Nevertheless, the selectivity behavior and regeneration of FeOOH are seldom studied. Therefore, we investigated the selectivity of FeOOH in a mixed solution of Co2+, Ni2+, and Pb2+ and proposed to enhance the capacity of FeOOH and regenerate it by using external charges. Without charge, the FeOOH electrode shows a Pb2+ uptake capacity of 20 mg/g. After applying a voltage of −0.2/+0.8 V, the uptake capacity increases to a maximum of 42 mg/g and the desorption ratio is 70%–80%. In 35 cycles, FeOOH shows a superior selectivity towards Pb2+ compared with Co2+ and Ni2+, with a purity of 97% ± 3% in the extracts. The high selectivity is attributed to the lower activation energy for Pb2+ sorption. The capacity retentions at the 5th and the 35th cycles are ca. 80% and ca. 50%, respectively, comparable to the chemical regeneration method. With industrially exhausted granular ferric hydroxide as the electrode material, the system exhibits a Pb2+ uptake capacity of 37.4 mg/g with high selectivity. Our work demonstrates the feasibility of regenerating FeOOH by charge and provides a new approach for recycling and upcycling FeOOH sorbent.

Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H2O)2V(µ-O)(PPA)2] (where PPA is phenylphosphonate). The crystal structure of [Cu(H2O)2V(µ-O)(PPA)2] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H2O)2V(µ-O)(PPA)2] has an indirect band gap of 2.19 eV. Photoluminescence (PL) spectra indicate a complex landscape of energy states with PL peaks at 1.8 and 2.2 eV. [Cu(H2O)2V(µ-O)(PPA)2] has estimated hybrid ionic and electronic conductivity values between 0.13 and 0.6 S m−1. Temperature-dependent magnetization measurements show that [Cu(H2O)2V(µ-O)(PPA)2] exhibits short range antiferromagnetic order between Cu(II) and V(IV) ions. [Cu(H2O)2V(µ-O)(PPA)2] is also photoluminescent with photoluminescence quantum yield of 0.02%. [Cu(H2O)2V(µ-O)(PPA)2] shows high electrochemical, and thermal stability.

We consider the two-species Vicsek model (TSVM) consisting of two kinds of self-propelled particles, A and B, that tend to align with particles from the same species and to antialign with the other. The model shows a flocking transition that is reminiscent of the original Vicsek model: it has a liquid-gas phase transition and displays micro-phase-separation in the coexistence region where multiple dense liquid bands propagate in a gaseous background. The interesting features of the TSVM are the existence of two kinds of bands, one composed of mainly A particles and one mainly of B particles, the appearance of two dynamical states in the coexistence region: the PF (parallel flocking) state in which all bands of the two species propagate in the same direction, and the APF (antiparallel flocking) state in which the bands of species A and species B move in opposite directions. When PF and APF states exist in the low-density part of the coexistence region they perform stochastic transitions from one to the other. The system size dependence of the transition frequency and dwell times show a pronounced crossover that is determined by the ratio of the band width and the longitudinal system size. Our work paves the way for studying multispecies flocking models with heterogeneous alignment interactions.

We study the active Potts model with either site occupancy restriction or on-site repulsion to explore jamming and kinetic arrest in a flocking model. The incorporation of such volume exclusion features leads to a surprisingly rich variety of self-organized spatial patterns. While bands and lanes of moving particles commonly occur without or under weak volume exclusion, strong volume exclusion along with low temperature, high activity, and large particle density facilitates jams due to motility-induced phase separation. Through several phase diagrams, we identify the phase boundaries separating the jammed and free-flowing phases and study the transition between these phases which provide us with both qualitative and quantitative predictions of how jamming might be delayed or dissolved. We further formulate and analyze a hydrodynamic theory for the restricted APM which predicts various features of the microscopic model.

Chemotaxis refers to the motion of an organism induced by chemical stimuli and is a motility mode shared by many living species that has been developed by evolution to optimize certain biological processes such as foraging or immune response. In particular, autochemotaxis refers to chemotaxis mediated by a cue produced by the chemotactic particle itself. Here, we investigate the collective behavior of autochemotactic particles that are repelled by the cue and therefore migrate preferentially towards low-concentration regions. To this end, we introduce a lattice model inspired by the true self-avoiding walk which reduces to the Keller-Segel model in the continuous limit, for which we describe the rich phase behavior. We first rationalize the chemically mediated alignment interaction between walkers in the limit of stationary concentration fields, and then describe the various large-scale structures that can spontaneously form and the conditions for them to emerge, among which we find stable bands traveling at constant speed in the direction transverse to the band.