Closing the Gap: Towards a Fully Continuous and Self-Regulated Kolbe Electrosynthesis.

In this article, we address the transition of the Kolbe electrolysis of valeric acid (VA) to n-octane as an exemplary electrosynthesis process from a batch reaction to a continuous, self-regulated process. Based on a systematic assessment of chemical boundary conditions and sustainability aspects, we propose a continuous electrosynthesis including a simple product separation and electrolyte recirculation, as well as an online-pH-controlled VA feeding. We demonstrate how essential performance parameters such as product selectivity (S) and coulombic efficiency (CE) are significantly improved by the transition from batch to a continuous process. Thus, the continuous and pH-controlled electrolysis of a 1 M valeric acid, starting pH 6.0, allowed a constantly high selectivity of around 47 % and an average Coulomb efficiency about 52 % throughout the entire experimental duration. Under otherwise identical conditions, the conventional batch operation suffered from lower and strongly decreasing performance values (Sn-octane, 60min =10.4 %, Sn-octane, 240min =1.3 %; CEn-octane, 60min =7.1 %, CEn-octane, 240min =0.5 %). At the same time, electrolyte recirculation significantly reduces wastes and limits the use of electrolyte components.

Enzymatic Upcycling of PET Waste to Calcium Terephthalate for Battery Anodes.

Biotechnological recycling offers a promising solution to address the environmental concerns associated with waste plastics, particularly polyethylene terephthalate (PET), widely utilized in packaging materials and textiles. To advance the development of a bio-based circular plastic economy, innovative upcycling strategies capable of generating higher-value products are needed. In this study, we enhanced the enzymatic depolymerization of waste PET by incorporating highly concentrated calcium ions (up to 1 m) to the hydrolytic reaction catalyzed by the best currently known enzyme LCCICCG . The presence of calcium ions not only improved the thermal stability and activity of the biocatalyst but also significantly reduced the consumption of base required to maintain optimal pH levels. Employing optimized conditions at 80 °C for 12 h, we successfully converted ≈84 % of the waste PET (200 g L-1 ) into solid hydrated calcium terephthalate (CaTP ⋅ 3H2 O) as the primary product instead of soluble terephthalate salt. CaTP ⋅ 3H2 O was easily purified and employed as a raw material for battery electrode production, exhibiting an initial reversible specific capacity of 164.2 mAh g-1 . Through techno-economic analysis, we conclusively demonstrated that the one-pot biocatalysis-based synthesis of CaTP is a superior PET upcycling strategy than the secondary synthesis method employing recycled terephthalic acid.

DistSNE: Distributed computing and online visualization of DNA methylation-based central nervous system tumor classification.

The current state-of-the-art analysis of central nervous system (CNS) tumors through DNA methylation profiling relies on the tumor classifier developed by Capper and colleagues, which centrally harnesses DNA methylation data provided by users. Here, we present a distributed-computing-based approach for CNS tumor classification that achieves a comparable performance to centralized systems while safeguarding privacy. We utilize the t-distributed neighborhood embedding (t-SNE) model for dimensionality reduction and visualization of tumor classification results in two-dimensional graphs in a distributed approach across multiple sites (DistSNE). DistSNE provides an intuitive web interface (https://gin-tsne.med.uni-giessen.de) for user-friendly local data management and federated methylome-based tumor classification calculations for multiple collaborators in a DataSHIELD environment. The freely accessible web interface supports convenient data upload, result review, and summary report generation. Importantly, increasing sample size as achieved through distributed access to additional datasets allows DistSNE to improve cluster analysis and enhance predictive power. Collectively, DistSNE enables a simple and fast classification of CNS tumors using large-scale methylation data from distributed sources, while maintaining the privacy and allowing easy and flexible network expansion to other institutes. This approach holds great potential for advancing human brain tumor classification and fostering collaborative precision medicine in neuro-oncology.

Insight into the Interaction of Furfural with Metallic Surfaces in the Electrochemical Hydrogenation Process.

Electrocatalytic hydrogenation of furfural on metal surfaces has become an important research subject due to the potential of the reaction product 2-methylfuran as a renewable energy resource. Identifying effective determinants in this reaction process requires a thorough investigation of the complex electrode-electrolyte interactions, which considers a variety of the influential components. In this work, in operando electrochemical Raman Spectroscopy and Molecular Dynamics simulations were utilized to investigate different characteristics of the interface layer in the electrocatalytic hydrogenation of furfural. Hereby, the influence of applied potentials, electrode material, and electrolyte composition were investigated in detail. The studied parameters give an insight into furfural's binding situation, molecular orientation, and reaction mechanism.

Carbon source priority and availability limit bidirectional electron transfer in freshwater mixed culture electrochemically active bacterial biofilms.

This study investigated, if a mixed electroactive bacterial (EAB) culture cultivated heterotrophically at a positive applied potential could be adapted from oxidative to reductive or bidirectional extracellular electron transfer (EET). To this end, a periodic potential reversal regime between - 0.5 and 0.2 V vs. Ag/AgCl was applied. This yielded biofilm detachment and mediated electroautotrophic EET in combination with carbonate, i.e., dissolved CO2, as the sole carbon source, whereby the emerged mixed culture (S1) contained previously unknown EAB. Using acetate (S2) as well as a mixture of acetate and carbonate (S3) as the main carbon sources yielded primarily alternating electrogenic organoheterotropic metabolism with the higher maximum oxidation current densities recorded for mixed carbon media, exceeding on average 1 mA cm-2. More frequent periodic polarization reversal resulted in the increase of maximum oxidative current densities by about 50% for S2-BES and 80% for S3-BES, in comparison to half-batch polarization. The EAB mixed cultures developed accordingly, with S1 represented by mostly aerobes (84.8%) and being very different in composition to S2 and S3, dominated by anaerobes (96.9 and 96.5%, respectively). S2 and S3 biofilms remained attached to the electrodes. There was only minor evidence of fully reversible bidirectional EET. In conclusion the three triplicates fed with organic and/or inorganic carbon sources demonstrated two forms of diauxie: Firstly, S1-BES showed a preference for the electrode as the electron donor via mediated EET. Secondly, S2-BES and S3-BES showed a preference for acetate as electron donor and c-source, as long as this was available, switching to CO2 reduction, when acetate was depleted.

Determining the Gibbs Energy Contributions of Ion and Electron Transfer for Proton Insertion in ϵ-MnO2.

Electrochemically active ϵ-MnO2 and ɣ-MnO2 as tunnel-type host-guest structures have been extensively studied by crystallography and electrochemical techniques for application in battery cathode materials. However, the Gibbs energies of the underlying ion and electron transfer processes across the electrode interfaces have not yet been determined. Here we report for the first time these data for ϵ-MnO2 . This was possible by measuring the mid-peak potentials in cyclic voltammetry and the open-circuit potentials under electrochemically reversible conditions.

Bidirectional electroactive microbial biofilms and the role of biogenic sulfur in charge storage and release.

The formation of combined electrogenic/electrotrophic biofilms from marine sediments for the development of microbial energy storage systems was studied. Sediment samples from the German coasts of the Baltic and the North Sea were used as inocula for biofilm formation. Anodic biofilm cultivation was applied for a fast and reproducible biofilm formation. North-Sea- and Baltic-Sea-derived biofilms yielded comparable anodic current densities of about 7.2 A m-2. The anodic cultivation was followed by a potential reversal regime, transitioning the electrode potential from 0.2 V to -0.8 V every 2 h to switch between anodic and cathodic conditions. The charge-discharge behavior was studied, revealing an electrochemical conversion of biogenic elemental sulfur as major charge-discharge mechanism. The microbial sequencing revealed strong differences between North- and Baltic-Sea-derived biofilms; however with a large number of known sulfur-converting and electrochemically active bacteria in both biofilms.

Direct and Indirect Electrooxidation of Glycerol to Value-Added Products.

In this work, different approaches for the direct and indirect electrooxidation of glycerol, a by-product of oleochemistry and biodiesel production, for the synthesis of value-added products and of intermediates for biofuel/electrofuel production, were investigated and compared. For the direct electrooxidation, metallic catalysts were used, whose surfaces were modified by promoters or second catalysts. Bi-modified Pt electrodes (Ptx Biy /C) served as model systems for promoter-supported electrocatalysis, whereas IrO2 -modified RuO2 electrodes were studied as catalyst combinations, which were compared under acidic conditions with the respective monometallic catalysts (Pt/C, RuO2 /Ti, IrO2 /Ti). Furthermore, inorganic halide mediators (chloride, bromide, iodide) and organic nitroxyl mediators (4-oxo-2,2,6,6-tetramethyl-piperidin-1-oxyl and 4-acetamido-2,2,6,6-tetramethyl-piperidin-1-oxyl) were evaluated for indirect electrooxidation. These different approaches were discussed regarding selectivity, conversion, and coulombic efficiency of the electrochemical glycerol oxidation.

How Comparable are Microbial Electrochemical Systems around the Globe? An Electrochemical and Microbiological Cross-Laboratory Study.

Invited for this month's cover is the collaborative work among Univ. of Milano-Bicocca, Ricerca sul Sistema Energetico S.p.A., Univ. degli Studi di Milano, Univ. of California Irvine, Univ. of New Mexico, CNRS Toulouse. Technische Univ. Braunschweig, Aquacycl LLC, J. Craig Venter Institute, Helmholtz-Centre for Environmental Research. The image shows a sketch of a microbial fuel cell and a target indicating the need of developing common standards for the field of microbial electrochemical technologies. The Full Paper itself is available at 10.1002/cssc.202100294.

How Comparable are Microbial Electrochemical Systems around the Globe? An Electrochemical and Microbiological Cross-Laboratory Study.

A cross-laboratory study on microbial fuel cells (MFC) which involved different institutions around the world is presented. The study aims to assess the development of autochthone microbial pools enriched from domestic wastewater, cultivated in identical single-chamber MFCs, operated in the same way, thereby approaching the idea of developing common standards for MFCs. The MFCs are inoculated with domestic wastewater in different geographic locations. The acclimation stage and, consequently, the startup time are longer or shorter depending on the inoculum, but all MFCs reach similar maximum power outputs (55±22 µW cm-2 ) and COD removal efficiencies (87±9 %), despite the diversity of the bacterial communities. It is inferred that the MFC performance starts when the syntrophic interaction of fermentative and electrogenic bacteria stabilizes under anaerobic conditions at the anode. The generated power is mostly limited by electrolytic conductivity, electrode overpotentials, and an unbalanced external resistance. The enriched microbial consortia, although composed of different bacterial groups, share similar functions both on the anode and the cathode of the different MFCs, resulting in similar electrochemical output.

Customizable design strategies for high-performance bioanodes in bioelectrochemical systems.

Bioelectrochemical systems (BESs) can fulfill the demand for renewable energy and wastewater treatment but still face significant challenges to improve their overall performance. Core efforts have been made to enhance the bioelectrode performance, yet, previous approaches are fragmented and have limited applicability, unable to flexibly adjust physicochemical and structural properties of electrodes for specific requirements in various applications. Here, we propose a facile electrode design strategy that integrates three-dimensional printing technology and functionalized modular electrode materials. A customized graphene-based electrode with hierarchical pores and functionalized components (i.e., ferric ions and magnetite nanoparticles) was fabricated. Owing to efficient mass and electron transfer, a high volumetric current density of 10,608 ± 1,036 A/m3 was achieved, the highest volumetric current density with pure Geobacter sulfurreducens to date. This strategy can be readily applied to existing BESs (e.g., microbial fuel cells and microbial electrosynthesis) and provide a feasibility for practical application.

Studying the Impact of Wall Shear Stress on the Development and Performance of Electrochemically Active Biofilms.

A laminar flow reactor was designed that provides constant and reproducible growth conditions for the bioelectrochemical observation of electroactive bacteria (EAB). Experiments were performed using four reactors in parallel to enable the comparison of EAB growth behavior and bioelectrochemical performance under different hydrodynamic conditions while simultaneously keeping biological conditions identical. With regard to the moderate flow conditions found in wastewater treatment applications, the wall shear stress was adjusted to a range between 0.4 mPa to 2.9 mPa. Chronoamperometric data indicate that early stage current densities are improved by a moderate increase of the wall shear stress. In the same way, current onset times were increasing slightly towards higher values of the applied wall shear stress. Long-term observations of EAB performance showed a decrease in current density and a leveling of the trend observed for the early stages of biofilm growth.

Development and characterization of a fiber optical fluorescence sensor for the online monitoring of biofilms and their microenvironment.

The growth of microorganisms on surfaces and interfaces as a biofilm is very common and plays important role in various areas such as material science, biomedicine, or waste treatment among others. Due to their inhomogeneous structure and the variance in the microorganism consortium, the analysis of biofilms represents a significant challenge. An online fluorescence sensor was developed that is able to measure the most important biological fluorophores (proteins, nicotinamide adenine dinucleotide, and flavin) in a noninvasive manner in biofilms, e.g. in bioelectrochemical applications. The sensor gives the opportunity to continuously draw conclusions on the metabolic state of the biofilm. The developed sensor has a diameter of 1 mm at the sensor tip and can be moved on and into the biofilm surface. In the first experiment, the measuring range of the sensor and the long-term stability could be determined and the system applicability was confirmed. In addition, measurements in biofilm-like structures could be performed. The formation of a wastewater-based biofilm was monitored using the developed sensor, demonstrating the functionality of the sensor in a proof-of-principle experiment.

Optimal Geometric Parameters for 3D Electrodes in Bioelectrochemical Systems: A Systematic Approach.

In this study, the performance of electroactive bacteria (EAB), cultivated inside tubular electrode ducts, is systematically investigated to derive predictions on the behavior of EAB under conditions limited by electrochemical losses. A modeling approach is applied to assess the influence of the electrochemical losses on the electrochemical performance and scaling characteristics of complex 3D structures, such as sponges and foams. A modular flow reactor is designed that provides laminar and reproducible flow conditions as a platform for the systematic electrochemical and bioelectrochemical characterization of 3D electrodes in bioelectrochemical systems (BES). The bioelectrochemical experiments are carried out in a set of reactors incorporating cylindrical electrodes exhibiting ducts of 1 cm length and different diameters ranging from 0.1 cm up to 1 cm. Single duct calculations are extrapolated to three dimensions through geometrical considerations; trends in 3D bioanode performance are demonstrated using the resulting simplified 3D structure. The combined experimental and modeling approach constitutes a framework for future studies on systematic electrode design.

The Limits of Three-Dimensionality: Systematic Assessment of Effective Anode Macrostructure Dimensions for Mixed-Culture Electroactive Biofilms.

This study analyzes the biofilm growth and long-term current production of mixed-culture, electrochemically active biofilms (EABs) on macrostructured electrodes under low-shear-force conditions. The channel dimensions were altered systematically in the range 400 µm to 2 mm, and the channel heights were varied between 1 and 4 mm to simulate macrostructures of different scales. Electrodes with finer-structured surfaces produced higher current densities in the short term owing to their large surface area but were outperformed in the long term because the accumulation of biomass led to limitations of mass transfer into the structures. The best long-term performance was observed for electrodes with channel dimensions of 1×4 mm, which showed no significant decrease in performance in the long term. Channels with a diameter of 400 µm were overgrown by the biofilm, which led to a transition from 3 D to 2 D behavior, indicating that structures of this scale might not be suitable for long-term operation under low-shear-stress conditions.

Long-Term Behavior of Defined Mixed Cultures of Geobacter sulfurreducens and Shewanella oneidensis in Bioelectrochemical Systems.

This work aims to investigate the long-term behavior of interactions of electrochemically active bacteria in bioelectrochemical systems. The electrochemical performance and biofilm characteristics of pure cultures of Geobacter sulfurreducens and Shewanella oneidensis are being compared to a defined mixed culture of both organisms. While S. oneidensis pure cultures did not form cohesive and stable biofilms on graphite anodes and only yielded 0.034 ± 0.011 mA/cm2 as maximum current density by feeding of each 5 mM lactate and acetate, G. sulfurreducens pure cultures formed 69 µm thick, area-wide biofilms with 10 mM acetate as initial substrate concentration and yielded a current of 0.39 ± 0.09 mA/cm2. Compared to the latter, a defined mixed culture of both species was able to yield 38% higher maximum current densities of 0.54 ± 0.07 mA/cm2 with each 5 mM lactate and acetate. This increase in current density was associated with a likewise increased thickness of the anodic biofilm to approximately 93 µm. It was further investigated whether a sessile incorporation of S. oneidensis into the mixed culture biofilm, which has been reported previously for short-term experiments, is long-term stable. The results demonstrate that S. oneidensis was not stably incorporated into the biofilm; rather, the planktonic presence of S. oneidensis has a positive effect on the biofilm growth of G. sulfurreducens and thus on current production.

Integrated Valorization of Desalination Brine through NaOH Recovery: Opportunities and Challenges.

The rising use of seawater desalination for fresh water production is driving a parallel rise in the discharge of high-salinity brine into the ocean. Better utilization of this brine would have a positive impact on the energy use, cost, and environmental footprint of desalination. Furthermore, intermittent renewable energy can easily power the brine utilization and, for reverse osmosis technology, the entire desalination plant. One pathway toward these goals is to convert the otherwise discharged brine into useful chemicals; waste could be transformed into sodium hydroxide or caustic soda (NaOH) and hydrochloric acid (HCl). In this Minireview, we discuss opportunities and challenges for integrated valorization of desalination brine through NaOH and HCl recovery.

Use of torsional resonators to monitor electroactive biofilms.

Whereas the study of interfaces and thin films with the quartz crystal microbalance (QCM) is well established, biofilms have proven to be a difficult subject for the QCM. The main problem is that the shear wave emanating from the resonator surface does not usually reach to the top of the sample. This problem can be solved with torsional resonators. These have a resonance frequency in the range of tens of kHz, which is much below the frequency of the thickness-shear QCMs. The depth of penetration of the shear wave is correspondingly larger. Data acquisition and data analysis can proceed in analogy to the conventional thickness-shear QCM. Torsional resonators may also be operated as electrochemical QCMs (EQCMs), meaning that a DC electrical potential may be applied to the active electrode and that shifts of frequency and bandwidth may be acquired in parallel to the electrical current. Here we report on the formation of mixed-culture biofilms dominated by the microorganism Geobacter anodireducens. The viscoelastic analysis evidences an increase in rigidity as the films grows. Potential sweeps on electroactive biofilms reveal a softening under negative potentials, that is, under conditions, where the layer's metabolism was slowed down by insufficient oxidative activity of the substrate. For comparison, biofilms were monitored in parallel with a conventional thickness-shear QCM.

Towards selective electrochemical conversion of glycerol to 1,3-propanediol.

1,3-propanediol (1,3-PD) is a bulk chemical with myriad applications in polymers, lubricants, cosmetics, foods industries and in the synthesis of heterocyclic compounds. Current commercial production of 1,3-PD involves a thermocatalytic process using acrolein (DuPont) and ethylene oxide (Shell) as starting feedstock. These feedstocks are petroleum-based and there are many efforts at using glycerol as low cost biomass-derived feedstock for 1,3-PD production. A number of catalyst designs and bacterial & fungal strains are being explored for respective catalytic and fermentation routes to glycerol-to-1,3-PD. However, the electrochemical method received little attention for the purpose. In this work, in order to explore the possibility of using partly refined glycerol byproduct of biodiesel production as feedstock, we investigated conversion and 1,3-PD selectivity of glycerol electrolysis in chloride media. We demonstrated selective glycerol-to-1,3-PD conversion using Pt or RuO2-based dsa as anode and Zn or Pb as cathode in NaCl and KCl at pH 1. This electrochemical glycerol-to-1,3-PD conversion is not only green, it is a potential process network loop between biodiesel production and chlor-alkali industry.

Design and Evaluation of a Boron Dipyrrin Electrophore for Redox Flow Batteries.

A boron dipyrrin (BODIPY) dye was designed as a molecular single-component electrophore for redox flow batteries. All positions of the BODIPY core were assessed on the basis of literature data, in particular cyclic voltammetry and density functional calculations, and a minimum required substitution pattern was designed to provide solubility, aggregation, radical cation and anion stabilities, a large potential window, and synthetic accessibility. In-depth electrochemical and physical studies of this electrophore revealed suitable cathodic behavior and stability of the radical anion but rapid anodic decomposition of the radical cation. The three products that formed under the conditions of controlled oxidative electrolysis were isolated, and their structures were determined by spectroscopy and comparison with a synthetic model compound. From these structures, a benzylic radical reactivity, initiated by one-electron oxidation, was concluded to play the major role in this unexpected decomposition.