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Advancing wastewater sustainability: Nafion-powered ammonium recovery

Wastewater treatment plant Bern

With global population growth and the resulting increase in environmental stress, the need for sustainable wastewater treatment is becoming ever more urgent. Traditional methods focus on removing pollutants but often overlook the opportunity to recover valuable resources. One such resource is ammonium. This nitrogen-containing molecule promotes growth and is a key component of fertilizers. When mishandled, such as through over-fertilization, ammonium becomes one of the main contributors to nitrogen pollution.

A promising solution lies in bioelectrical systems. This umbrella term refers to innovative technologies that not only purify wastewater but also recover resources like ammonium. At the same time, bioelectrical systems generate clean energy such as electricity or biogas. The technology is based on galvanic cells, where the two cell chambers are often separated by a membrane. High-performance cation exchange membranes enable precise ion transport and system stability. The premium product among cation exchange membranes is Nafion, such as our Nafion 115 membrane.

At Frontis Energy, we have demonstrated that bioelectrochemical systems can remove ammonium from wastewater, offering an energy-efficient alternative to the energy-intensive Haber-Bosch process. To validate this concept, we developed microbiological electrolysis cells populated with microorganisms from oxygen-deprived marine sediments off the coast of Namibia. These sediments are naturally rich in ammonia and low in organic carbon, ideal conditions for microbes capable of anaerobic ammonium oxidation. For comparison, we also used conventional municipal wastewater to populate the electrodes.

Maintaining anoxic conditions was crucial to avoid nitrification, a process that transfers electrons directly to oxygen, bypassing the anode and resulting in energy loss and reduced hydrogen production. Instead, we regulated the anode potential between +150 mV and +550 mV, well below the redox potential required for water oxidation (+820 mV). This configuration enabled the oxidation of ammonium to nitrogen gas (N₂) at the anode, while hydrogen (H₂) or methane gas was produced at the cathode.

Central to this process is Nafion 115, a membrane made of perfluorosulfonic acid polymers (PFSA polymers). Its exceptional proton conductivity, chemical resistance, and mechanical robustness make it ideal for demanding wastewater environments. Nafion 115 acts like a selective gate, allowing ammonium ions (NH₄⁺) to migrate from the anode to the cathode while blocking competing ions and maintaining anoxic conditions. This selective transport, driven by electric field gradients and concentration differences, ensures efficient nutrient recovery and stable performance of the bioelectrical system.

A practical validation of this technology comes from our earlier report, in which researchers developed a two-chamber, anoxic bioelectrical reactor that continuously removed ammonium at a rate of about 5 g/m³/day. Their system converted over 97% of the ammonium directly into nitrogen gas. This transformation occurred without the formation of harmful byproducts like nitrite or NOx gases. Particularly impressive was the energy consumption, just 0.13 kWh per kilogram of nitrogen removed. That is a 35-fold reduction compared to conventional aeration, which typically requires around 5 kWh/kg.

These results highlight the transformative potential of bioelectrical systems. As mentioned earlier, significant energy is used to remove nitrogen from wastewater, only to make it available again via the Haber-Bosch process, accounting for 1–2% of global energy consumption. Bioelectrical systems offer a circular alternative: by coupling ammonium oxidation with hydrogen production, wastewater treatment plants could become net energy producers. The generated hydrogen and biogas can be used directly for electricity generation and ultimately to reduce greenhouse gas emissions.

With the right biofilms, well-controlled electrode potentials, and robust membranes like Nafion 115, ammonium can serve as a clean, resource-efficient alternative to water electrolysis. This underscores the potential of bioelectrical systems to build a circular water economy, where waste is treated as a resource.

This technology reflects Frontis Energy’s commitment to promoting clean, efficient, and circular solutions that turn ecological challenges into sustainable opportunities.

Image: Wastewater treatment plant Bern

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Stability of anion exchange membranes for electrolysis

Electrolyzer in China

Energy security and climate change are among the greatest challenges of our time. To reduce dependence on fossil fuels, renewable energy sources are emerging as key solutions for sustainable energy production. To this end, scalable solutions are essential for storing and transporting renewable energy. Hydrogen produced in water electrolyzers and reconverted into electricity in fuel cells can help balance the seasonal variability of renewable energy.

Fuel cells have the potential to significantly contribute to the decarbonization of the transport sector. Transport of people and goods accounts for almost one‑third of global greenhouse gas emissions. Despite this potential, the widespread adoption of modern fuel cells and electrolyzers remains limited due to high investment costs. This is mainly due to expensive noble‑metal catalysts and perfluorinated proton exchange membranes.

This challenge has sparked growing interest in anion exchange membranes. Under alkaline conditions, they offer several advantages:

  • Use of non‑noble metal catalysts thanks to non‑corrosive conditions
  • More sustainable membrane materials

However, there are hurdles to their introduction, particularly their short lifetime under alkaline conditions and oxidative stress. The formation of hydrogen peroxide and hydroxyl radicals under alkaline conditions is responsible for the accelerated degradation of polymer membranes. Investigation radical‑induced degradation of anion exchange membranes is therefore of central importance.

Hence, efficient radical generation in the laboratory is required. Current methods such as thermal decomposition or UV activation of hydrogen peroxide are inefficient and prone to side reactions, limiting their relevance to real operating conditions. Immersion in oxygen‑saturated alkaline solutions has provided useful insights, but cannot distinguish between natural membrane degradation and radical‑accelerated breakdown.

Radioactivity and electromagnetic pulse radiation allow precise control of radical formation but require expensive, specialized infrastructure. Affordable and practical solutions are needed to study radicals under realistic laboratory conditions.

Researchers from SINTEF in Norway and ETH Zurich have addressed this challenge. They introduced adapted photochemical methods to generate radicals and study their influence on the stability of anion exchange membranes independently of other degradation processes. The results were recently published in Membranes.

By irradiating aqueous potassium nitrite solutions or titanium oxide suspensions with UV light at 365 nm, hydroxyl radicals or a combination of hydroxyl and superoxide radicals were successfully generated. Tests on three commercial anion exchange membranes – PiperION®‑40 (PiperION), FM‑FAA‑3‑PK‑75 (Fumasep), and PNB‑R45 (Polynorbornene) – showed clear differences in durability. As expected, thinner, non‑reinforced membranes degraded faster than thicker, reinforced ones, likely due to the limited penetration depth of highly reactive radicals.

Both methods proved to be practical, affordable, and accessible tools for evaluating the stability of anion exchange membranes against radical attack. Photochemical radical generation was thus a viable way to study radical‑induced degradation under controlled conditions. The nitrite‑based approach selectively generated hydroxyl radicals, while titanium oxide suspensions produced both hydroxyl and superoxide radicals. Longer irradiation intensified membrane damage, clearly demonstrating the critical role of radicals in membrane decomposition. Experiments at pH 10 enabled differentiation between natural and radical‑driven causes.

Beyond laboratory use, both methods are also of industrial relevance. Combined with low‑cost laboratory equipment, they provide widely applicable and reproducible tools for evaluating commercial and prototype anion exchange membranes. By reducing costs and extending durability tests under realistic conditions, the development of robust anion exchange membranes for fuel cells and electrolyzers can be accelerated.

Frontis Energy is part of the mission to provide cost‑effective solutions for the development of efficient energy conversion technologies. In doing so, we strengthen the global transition to clean, resilient, and sustainable energy systems.

Solyom, P.; Nauser, T.; Nemeth, T. Photochemical Methods to Study the Radical-Induced Degradation of Anion-Exchange Membranes. Membranes 2025, 15, 305. https://doi.org/10.3390/membranes15100305

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Advances in ammonium recovery with bioelectrical systems

DOI: 10.13140/RG.2.2.16014.22082

In recent decades, the focus of wastewater treatment has shifted from mere disposal to the recovery of valuable resources. This approach aims to harness energy and nutrients found in wastewater. Among emerging technologies are bioelectrical systems, which can recover not only energy and carbon but also valuable compounds like ammonium. Nitrogen bound in ammonium is a key component of fertilizers. Today, two-thirds of this resource are produced through the highly energy-intensive Haber-Bosch process using natural gas extracted from air. Fertilizer production significantly contributes to anthropogenic CO₂ emissions and, ultimately, to global warming.

Bioelectrical systems for ammonium recovery are classified into microbial fuel cells and microbial electrolysis cells. In both, electrogenic microorganisms oxidize organic matter in wastewater into carbon dioxide and protons. Exoelectrogens, also known as anode-respiring bacteria, use the anode as an electron acceptor instead of oxygen, thereby gaining energy for their metabolic processes.

By combining microbial activity with electrochemical processes, chemical reactions in wastewater treatment are catalyzed efficiently. This novel biocatalytic application still faces challenges in terms of optimization for practical use. At Frontis Energy, we have already demonstrated through a patented process that ammonium can be effectively removed from wastewater using bioelectrical systems. We are currently working on scaling this method for industrial deployment. However, a comprehensive understanding of the underlying processes and recovery mechanisms is still lacking.

A new study conducted by the Autonomous University of Barcelona investigated the development and optimization of bioelectrical systems aimed at recovering ammonium from wastewater in an energy-efficient and concentrated form. The findings were recently published in Bioelectrochemistry. Using a three-chamber configuration with a hydrophobic membrane, the researchers systematically examined the influence of different levels of electric current and ammonium concentrations on recovery efficiency. The system achieved its highest ammonium recovery rate of 55 g/m²/day at a current of 75 mA. Overall, a 97% removal of ammonium from a 0.3% solution was attained.

Notably, electrons flow from the anode to the cathode via an external circuit, where they react with an electron acceptor. In ammonium recovery systems, ammonium ions migrate from the anode to the cathode through a cation exchange membrane, driven by concentration gradients and the electric field, allowing them to accumulate in the cathode chamber.

While this ion transport mechanism supports efficient ammonium recovery, the researchers found that high-performance operation led to material wear at the cathode. This highlights the need to balance operational intensity with material durability. Consequently, the team explored different cathode materials and voltages. Stainless steel electrodes operated at 1.4 V yielded the best results, achieving a removal rate of 21 g/m²/day and a recovery rate of 17 g/m²/day, primarily due to enhanced cation migration resulting from higher current density.

Long-term experiments revealed that higher ammonium concentration in the anolyte significantly improves selective migration of ammonium ions through the cation exchange membrane, further boosting system performance. Operating at 1.4 V increased recovery efficiency and reduced energy consumption per gram of nitrogen—making the process more cost-effective and environmentally friendly.

These insights underscore the practical potential of bioelectrical systems as a pioneering solution for sustainable nitrogen recovery. By fine-tuning material selection, system design, and operational parameters, high ammonium removal and recovery rates can be achieved with minimal energy input.

From an industrial perspective, this study represents a scalable advance in resource recovery within existing wastewater treatment infrastructures. If scaled, the technology could reduce reliance on the energy-intensive Haber-Bosch process.

Since concentrated ammonium is a commercially viable product, its recovery reduces operational costs for wastewater treatment plants. If the scaled-up process maintains its long-term stability and low energy demand, these would be compelling arguments for adopting bioelectrical technologies as part of a circular economy.

At Frontis Energy, we see great potential in scaling this technology and making a meaningful contribution to sustainable wastewater treatment.

Ul, et al. 2025, Electrochemical and bioelectrochemical ammonium recovery from N-loaded streams using a hydrophobic membrane, Bioelectrochemistry, Volume 166, 109013, 10.1016/j.bioelechem.2025.109013.

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Improved membrane configurations for capacitive flow-electrode desalination

DOI: 10.13140/RG.2.2.19476.16002

With the growing global scarcity of drinking water, the demand for practical and energy-efficient desalination methods is on the rise. Among potential solutions are osmotic desalination methods like capacitive deionization and its advanced form, flow-electrode capacitive deionization (FCDI). Flow electrodes are streaming electrodes composed of conductive particles suspended in a liquid. When electrically charged, these particles behave like capacitors and gain capacitive properties.

In flow-electrode deionization, flowable carbon electrodes are combined with ion-exchange membranes. The use of membranes enables continuous and efficient desalination. Membranes induce a selective transport of charged ions, allowing oppositely charged ions (counterions) to pass while repelling similarly charged ions (co-ions). This selective ion transport is essential for targeted salt removal from the feed stream.

Research advancements have improved membrane properties, associated ion selectivity, and the design of galvanic cells, leading to practical applications. For example, flow-electrode deionization was tested for industrial feasibility in a pilot plant in 2023. Performance optimization depends significantly on understanding how ion transport behaves with different membrane configurations. Ion-exchange membranes play a key role in controlling ion movement. Certain membrane arrangements, such as membrane “sandwiches” made of anion and cation exchange membranes, significantly accelerated desalination. While promising results were achieved with simple salt solutions like NaCl and KCl, mixtures of diverse ions, as found naturally in seawater, are more challenging.

Researchers from RWTH Aachen University recently investigated how different ion-exchange membrane arrangements affect selective ion removal from complex salt mixtures, such as those containing carbonate and sulfate ions, in flow-electrode deionization. Their findings were published in the journal Desalination. Two deionization modules with different membrane setups were analyzed. Membrane layers were tested with the cation membrane on the inside and the anion membrane on the outside, and vice versa. Both configurations delivered similar desalination performance, but the time to reach a stable state varied depending on the arrangement and the flow electrode’s buffering capacity.

The tested anion exchange membranes showed a higher affinity for sulfate ions than for carbonate ions, which delayed stabilization in some cases. Strategies like reducing electrode volume and steering specific ions along the electrode path helped reach the steady state more quickly. These findings underscore the importance of membrane selectivity, electrode properties, and system design in enhancing the performance of flow-electrode deionization, especially for mixed-ion water sources.

The effectiveness of the process depends not just on reaching a steady desalination state but also on managing ion selectivity and system adaptation. With saltwater containing multiple cations and anions, membrane arrangement alone is not enough to achieve the desired results. To tackle these challenges, strategies like membrane coatings or modifying electrode properties must be considered.

The researchers also addressed evaluation methods in their study. Interestingly, measuring conductivity alone is not sufficient to assess desalination performance. While it indicates total salt concentration, it does not reflect changes in salt composition. Therefore, more precise evaluation methods are needed to meet specific requirements.

These advances are crucial for optimizing flow-electrode deionization performance and meeting the growing demand for efficient, adaptable water treatment technologies. At Frontis Energy, we are excited to see how this groundbreaking technology will scale in the future.

Mankertz, Theis, Linnartz, Wessling, 2025, Membrane arrangement influences time to steady state in FCDI with multi-ionic salt solutions, Desalination, Volume 613, 118939, DOI: 10.1016/j.desal.2025.118939.

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Electrolytic water splitting for binders in building material

DOI: 10.13140/RG.2.2.27780.18562

The oceans are rich in magnesium resources, which that could be used in the production of construction materials. Sorel cement (magnesium cement), for example, can be used in interior building applications as an alternative to screed. Extracting magnesium from seawater traditionally requires a highly energy-intensive calcination process to isolate magnesium oxide (magnesia). The innovative method of electrolysis-controlled water splitting can bypass this process, significantly reducing CO₂ emissions.

To obtain the precursor of magnesia, magnesium hydroxide (Mg[OH]₂), an alkaline solution must be produced. While previous research has investigated electrochemical methods for hydroxide production, few studies have combined efficient alkali synthesis with the direct precipitation of magnesium hydroxide to make magnesia for low-carbon cement. This critical knowledge gap in optimizing energy and material efficiency has now been addressed.

A new study led by a research team at Columbia University used electrochemical water splitting at low voltages (1.6–2.0 V). Hydroxide ions (OH⁻) were generated from seawater through hydrogen production. This led to the direct precipitation of magnesium hydroxide. The findings were recently published in the journal Desalination. This new approach reduces energy intensity by 52–78%. Normally, the energy consumption per ton of MgO is 0.56 MWh. With the new method, carbon emissions per ton of magnesia can be reduced by up to 0.41 tons of CO₂.

To further improve production efficiency, the nanostructure of magnesium hydroxide was optimized using urea as a crosslinker. This enhanced its reactivity, porosity, and specific surface area. At an optimal urea concentration of 0.2 mol/L, magnesia particles exhibited excellent binding properties. The researchers attributed this to the sealing effects of rosette-shaped dypingite and rod-shaped nesquehonite. According to the authors, the formation of these minerals facilitates CO₂ incorporation and enhances carbonate hardening.

Advances in symmetric electrochemical systems, as demonstrated in this study, result in up to a 78% reduction in energy demand for the production of alkaline solutions. This gives these methods the potential to serve as viable alternatives to traditional processes. The further optimization of electrodes and electrolytes represents a pioneering approach to the carbon-neutral production of building materials and alkalis. Additionally, this method highlights how construction material manufacturing can efficiently lead to large-scale CO₂ mineralization. As a result, the greenhouse gas can be permanently removed from the atmosphere.

The industrial scaling of electrochemical alkali production can reduce operating costs, minimize environmental impact, and improve the properties of low-carbon building materials. The economic aspects of this manufacturing process are particularly noteworthy, as the demand for efficient binding materials continues to grow.

At Frontis Energy, we are committed to promoting sustainable and economically viable energy solutions. Research like this provides valuable insights and innovations to support such sustainable advancements.

Chu. Yang, Unluer, 2025, Energy-efficient calcination-free Mg cement recovered from desalination brine, Desalination, Volume 610, 118928, 10.1016/j.desal.2025.118928.

Image: Pixabay

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From waste heat to ultrapure water: A new technology transforming renewable hydrogen

DOI: 10.13140/RG.2.2.34925.24809

Hydrogen (H₂), produced using renewable energy, has emerged as a possible alternative to fossil fuel. This versatile molecule can serve as an energy carrier, an efficient storage solution, and a sustainable feedstock for transportation, chemical processing, and energy systems worldwide.

Unlike fossil fuels, hydrogen produces no harmful emissions when used. It can be generated using electrolyzers running on renewable energy and abundant water as feedstock. It then becomes a renewable and sustainable energy source, reducing reliance on depleting fossil fuel reserves, helping combat climate change. Consequently, hydrogen production has become a key priority on the political agenda of numerous countries.

However, the water used in electrolyzers must be ultrapure in order to protect the electrodes of electrolyzers from poisoning and avoid chloride oxidation to chlorine. Abundant seawater adds several challenges when directly fed to electrolyzer plants for hydrogen production, making highly pure water, specifically ultrapure water, an expensive necessity. Ultrapure water is produced in a series of steps, including pretreatment to remove suspended solids and desalination to eliminate salts, organics, and colloidal particles. Polishing techniques such as deionization, degasification, and ultraviolet treatment are then used to achieve the required quality. Among these processes, desalination is particularly critical for removing most impurities.

Reverse osmosis, especially seawater reverse osmosis, is a widely used desalination technology but has notable drawbacks, such as requiring high-pressure operation (high energy consumption), intensive pretreatment, and producing concentrated brine, which can harm marine ecosystems when discharged. Membrane distillation has gained attention as an alternative for producing high-quality water and supporting recovery applications. It operates at lower temperatures and has the ability to utilize waste heat.

Membrane distillation is a thermal separation process where a vapor pressure difference across a hydrophobic membrane causes liquid particles to phase change and pass through as gas. Operating at ambient pressure and utilizing low-temperature heat sources (<90 °C), membrane distillation offers significant advantages. However, research on membrane distillation as a viable alternative to reverse osmosis for ultrapure water production remains limited, particularly in areas such as module design and techno-economic analysis.

A group of researchers at the Fraunhofer Institute for Solar Energy Systems (ISE) in Freiburg, Germany, has explored the potential of membrane distillation as a cost- and energy-efficient alternative to reverse osmosis for producing ultrapure water for proton exchange membrane (PEM) electrolyzers. The findings were recently published in the Desalination Journal. They introduced membrane distillation as a possible alternative to reverse osmosis for ultrapure water production. But here is the twist: the membrane distillation system ingeniously taps into waste heat from a 5 MW proton exchange membrane electrolyzer, transforming what would typically be an efficiency liability into an asset for sustainability. So far, their results are impressive—membrane distillation not only produces exceptional distillate (<3 μS/cm) but does so at a cost ranging from €2.33 to €2.85 per ton of distillate, compared to reverse osmosis’s €2.80 to €5.51. Using membrane distillation, seawater desalination could be 50% or more cheaper.

Economic analyses highlight that membrane distillation’s cost-effectiveness is driven by its low electrical energy requirements and optimized short-channel module design. Its impressive energy efficiency, enabled using low-grade thermal energy, establishes membrane distillation as a highly versatile and environmentally friendly solution that aligns seamlessly with the vision for renewable hydrogen production. This study positions membrane distillation as more than just an alternative to reverse osmosis: it is a smarter and greener approach to ultrapure water production.

Their findings have the potential to reshape the industrial approach to ultrapure water production. By demonstrating an efficient use of waste heat and providing a more economical solution, it offers industries a pathway to lower operational costs while advancing sustainability. This aligns particularly well with sectors striving for greener operations, such as renewable hydrogen production and other energy-intensive applications. Moreover, the adoption of membrane distillation could catalyze innovation in system design and integration, encouraging industries to optimize processes and reduce dependence on traditional, energy-intensive methods. This shift can contribute to broader sustainability goals and improve the economic feasibility of renewable energy initiatives.

At Frontis Energy, we are committed to advancing sustainable and green energy solutions by embracing innovative technologies like membrane distillation, bringing us closer to a sustainable future.

Schwantes et al. 2025 Thermally driven ultrapure water production for water electrolysis – A techno-economic analysis of membrane distillation, Desalination, Volume 608, 118848, DOI: 10.1016/j.desal.2025.118848.

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Unlocking the potential of conducting polymers for sustainable water treatment and energy solutions

DOI: 10.13140/RG.2.2.24586.94404

Carbon based materials have a broad range of applications such as energy storage and conversion, electronics, nanotechnology, water purification, and catalysis. They are made of an element which is available everywhere.

In recent times, the electrochemical features of carbon-based electrodes are being enhanced by using conducting polymers. Carbon cloth, woven from carbon microfibers, serves as a promising carbon-based electrode, which acts as a durable and cost-effective medium for facilitating electrochemical reactions that degrade pollutants and improve water quality. These electrodes, notable for their mechanical flexibility, strength, and cost-effectiveness, are employed in processes such as electrochemical oxidation, microbial fuel cells, and other advanced wastewater treatment technologies.

Due to a few limitations of pristine carbon cloth electrodes such as low specific capacitance and limited wettability associated with its inherent hydrophobicity, scientists conduct research to improve the modern electrodes. For instance, since wettability is crucial for for immersing the electrode surface in liquid and ensuring interaction with contaminants, enhancing it is always beneficial for the process. Improving the performance of carbon cloth electrodes could lead to more efficient treatment, faster reaction times, and better overall performance.

A research group at San Diego State University undertook the task of addressing these limitations by making conformal conducting polymer films on carbon fibers via oxidative chemical vapor deposition (oCVD) method. They recently published their results in the Advanced Material Interface Journal. With antimony pentachloride (SbCl5) as the oxidant, they developed a highly uniform coating of poly(3,4-ethylenedioxythiophene) (PEDOT) on three-dimensional porous fibers. The oCVD technique ensures uniform coatings while preserving the geometric and functional properties of the carbon cloth, making it a promising approach for enhancing electrochemical performance.

The PEDOT-coated carbon cloth electrodes achieved a remarkable improvement in specific capacitance and pseudocapacitance compared to pristine carbon cloth. Depending on the deposition temperature, the oCVD PEDOT-coated electrodes showed a 1.5- to 2.3-fold enhancement in specific capacitance. Notably, the electrode fabricated at a deposition temperature of 80 °C exhibited the highest specific capacitance and superior electrochemical performance. Adjusting the deposition temperature to optimize performance can help tailor carbon cloth electrodes for specific wastewater treatment needs.

The investigation underscores the effectiveness of the oCVD method in addressing the limitations of carbon cloth electrodes and expanding their potential applications in wastewater treatment and electrochemical energy storage devices. Furthermore, the researchers showed that PEDOT-coated carbon cloth can be applied as supercapacitors, where flexibility and high capacitance are critical. It should be noted that the study not only showcases significant advancements in material design but also open new avenues for optimizing electrode performance for diverse applications.

Overall, the findings emphasize the growing potential of advanced electrode technologies in addressing industrial challenges. By improving the functionality of carbon-based electrodes through novel material coatings, industries can achieve more efficient and tailored solutions for both wastewater treatment and energy storage. The ability to fine-tune electrode properties to meet specific requirements offers a pathway toward the development of highly efective and cost-efficient technologies, which could be a game-changer for sectors focused on sustainability and resource management. As these innovations continue to evolve, they have the potential to significantly improve operational efficiency and environmental impact across various industries. For example, in wastewater treatment, electrochemical processes such as electrocoagulation, electrooxidation, or electroreduction are often used to remove contaminants.

At Frontis Energy, we believe that improvements and customization can aid in designing electrodes tailored to specific contaminants or types of wastewater.

Heydari Gharahcheshmeh and Chowdhury, 2024, Enhancing Capacitance of Carbon Cloth Electrodes via Highly Conformal PEDOT Coating Fabricated by the OCVD Method Utilizing SbCl5 Oxidant, Advanced Materials Interfaces, 11, 2400118. DOI: 10.1002/admi.202400118.

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Complex interaction between nitrogen emissions and global warming

Nitrogen compounds are essential for life on Earth. The use of fossil fuels and artificial fertilizers have led to a significant increase in reactive nitrogen available to the biosphere. This increase has far-reaching and well-researched effects on ecosystems, biodiversity and health. Air pollution can lead to premature deaths and nitrogen compounds may play an important role. Previous studies have only inadequately researched the effects of reactive nitrogen on the global climate system since industrialization.

A new study by the Max Planck Institute for Biogeochemistry in Jena is now closing this knowledge gap. The researchers modeled the terrestrial biosphere and global atmospheric distribution of nitrogen. They then combined the results with findings from atmospheric chemistry. This combination enabled them to come up with a new and comprehensive assessment of the climate impact of anthropogenic reactive nitrogen. The results were recently published in the renown scientific journal Nature.

Man emits a number of nitrogen compounds. Some of these, such as nitrous oxide (N2O, laughing gas), are greenhouse gases. Others, such as fine dust particles that reflect solar radiation, have a cooling effect on the climate. These effects were also described in the present the study. Significant warming due to increasing concentrations of the greenhouse gases nitrous oxide  and ozone (O3) were reported. In contrast, several processes that contribute to the cooling effect of nitrogen were also described. In addition to particulate matter, these processes include chemical reactions that lead to a shorter residence time of the greenhouse gas methane in the atmosphere, as well as an increased uptake of carbon dioxide (CO2) by the terrestrial biosphere due to the fertilizing effect of nitrogen.

If all global warming and cooling processes caused by the reactive nitrogen are combined, a net cooling effect is the result. This new result suggests that nitrogen emissions have compensated for about one sixth of the global warming to date caused by the increase in CO2 over the industrial period.

The new results are also important for future strategies for nitrogen regulation in the context of climate protection policy. In most scenarios, nitrous oxide emissions from farming remained high due to the continued use of fertilizers in agriculture and thus the warming influence of this gas. Scenarios that are compatible with the climate goals of the Paris Agreement require an end to CO2 emissions from fossil fuels. This also reduces the release of reactive nitrogen from fossil sources and its harmful effects on health and biodiversity, but also eliminates its cooling effect. The researchers therefore expect a slightly warming contribution from total nitrogen for these climate protection scenarios, but this is far less than the warming from the unchecked consumption of fossil fuels.

The study underlines the urgency of finally stopping emissions from fossil fuels and using fertilizers more specifically. This would not only slow down global warming, but also reduce the burden of harmful ozone and particulate matter concentrations for all of us in rural areas and in cities. New technologies are needed to reduce harmful nitrogen emissions while making good use of beneficial nitrogen. At Frontis Energy we have developed such a technology. Our patented process removes ammonia from wastewater while producing useful carbon neutral biogas. Using this technology, harmful nitrous oxide emissions can be reduced.

Picture: Smog over Guangzhou, China

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Terrestrial vegetation and soils absorb up to 30% more CO2

A significant part of the scientific community is investigating in impact of GHG emissions, and in particular CO2, on our past, present, and future climate. To model our future climate, researchers use CO2 emissions to estimate the future climate of our planet. They predict how much CO2 industry and households can emit to remain within the set 1.5°C target. The central question therefore is: How much of the emitted CO2 actually remains in the atmosphere? How much is metabolized or otherwise bound?

It seems the models have so far underestimated the capacity of biomass to incorporate CO2. That is because the models have now received a major upgrade from an analysis of radiocarbon data from nuclear bomb testing in the 1960s, which suggests that terrestrial ecosystems are capable of absorbing more CO2 than previously thought. Does that mean that the earth copes with more emissions?

Researchers  at the Worcester Polytechnic Institute in Massachusetts found that plants are currently absorbing 80 million tons of CO2 each year. They published their finding in a recent article in the renown magazine Science. That is 30% more than previously assumed.

The initial idea was to take a closer look at the remnants of the nuclear tests in the 1950s and 1960s. Carbon dioxide molecules are made of carbon and oxygen. The radioactive substances that atomic bombs have left all over the world is also a radioactive carbon (14C). Like ordinary carbon (12C), the radioactive version is a possible component in CO2. After the atomic bombing tests, 14C got into the terrestrial biosphere through the photosynthesis of plants along with 12C. So one studies how 14C was enriched, the rates of the CO2 uptake in plants reveal how much carbon is captured.

Animals that feed on plants take in the same CO2 into their organism, as well as fungi and soil bacteria. Through decaying biomass in soil, carbon is then again released into the atmosphere in the form of CO2 and the cycle closes.

However, the question of is how much CO2 from the air goes into the ground and in is bound in biomass long term is anything but trivial. The analyzes of radioactive carbon now show slightly less 14CO2 in the atmosphere shortly after the nuclear tests. That is, plants worldwide would bind 80 gigatons carbon per year. So far, climate researchers assumed that storage performance was 43 to 76 gigatons.

The current assumptions were wrong due to the fact that mainly tree trunks were used for the calculation. Carbon stored in wood has been bound for many decades or centuries. The new study looked at non-wood biomass such as leaves, which also store a large proportion of carbon. Plus, extensive  underground plant biomass received hitherto too little attention. As a rule, underground biomass is comparable to what’s found above ground. In particular, only the woody roots were taken into account, but not the fine rhizosphere which has even more mass and accordingly binds more carbon.

Eighty gigatons are not only significantly more than is used in the common climate change forecasts. It is also twice as much as the annual man-made CO2 emissions (37.2 billion tons).

Unfortunately, this does not mean that there is nothing to worry about. Living creatures also use biomass as a fuel. Almost the same amount of CO₂ is released again when plants lose their leaves in autumn, which then serve soil creatures as a source of food. These natural CO2 emissions from the biosphere have accelerated more since the 1960s.

Overall, photosynthesis can get only 30% of the total man-made CO2 emissions from the atmosphere and can therefore not make up for fossil fuel consumption. With large natural areas available for photosynthesis more CO2 could be extracted from air. In consequence, more and not fewer forests and meadows need to be re-naturalized.

Some climate models are based on wrong assumptions. And yet, the more important carbon storage is not on land, but in the water. CO2 dissolves better there and countless micro-algae in the oceans also carry out photosynthesis. Carbon is very popular as building material for shells. In total, the oceans 16 times more carbon than the biosphere on land.

The key findings include:

  • Terrestrial vegetation and soils might absorb up to 30% more CO2 than what was estimated by earlier models.
  • The carbon storage in these ecosystems is more temporary than once believed, implying that man-made CO2 may not remain in the terrestrial biosphere as long as current models suggest.
  • The discrepancy in the models is due to underestimating the carbon stored in short-lived or non-woody plant tissues, as well as the extensive underground parts of plants, like fine roots.

The implications of these findings are significant for climate predictions and crafting effective climate policies. It highlights the need for more accurate representation of the global carbon cycle in climate models. While this increased uptake of CO2 by vegetation is a positive sign, it does not negate the urgency of reducing carbon emissions to combat climate change.

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Producing liquid bio-electrically engineered fuels from CO2

At Frontis Energy we have spent much thought on how to recycle CO2. While high value products such as polymers for medical applications are more profitable, customer demand for such products is too low to recycle CO2 in volumes required to decarbonize our atmosphere to pre-industrial levels. Biofuel, for example from field crops or algae has long been thought to be the solution. Unfortunately, they require too much arable land. On top of their land use, biochemical pathways are too complex to understand by the human brain. Therefore, we propose a different way to quickly reach the target of decarbonizing our planet. The proce­dure begins with a desired target fuel and suggests a mi­crobial consortium to produce this fuel. In a second step, the consortium will be examined in a bio-electrical system (BES).

CO2 can be used for liquid fuel production via multiple pathways. The end product, long-chain alcohols, can be used either directly as fuel or reduced to hydrocarbons. Shown are examples of high level BEEF pathways using CO2 and electricity as input and methane, acetate, or butanol as output. Subsequent processes are 1, aerobic methane oxida­tion, 2, direct use of methane, 3 heterotrophic phototrophs, 4, acetone-butanol fermentation, 5, heterotrophs, 6, butanol di­rect use, 7, further processing by yeasts

Today’s atmospheric CO2 imbalance is a consequence of fossil carbon combus­tion. This real­ity requires quick and pragmatic solutions if further CO2 accu­mulation is to be prevented. Direct air capture of CO2 is moving closer to economic feasibility, avoid­ing the use of arable land to grow fuel crops. Producing combustible fuel from CO2 is the most promis­ing inter­mediate solution because such fuel integrates seamlessly into existing ur­ban in­frastructure. Biofuels have been ex­plored inten­sively in re­cent years, in particular within the emerging field of syn­thetic biol­ogy. How­ever tempt­ing the application of genetically modified or­ganisms (GMOs) ap­pears, non-GMO technology is easier and faster to im­plement as the re­quired microbial strains al­ready exist. Avoiding GMOs, CO2 can be used in BES to produce C1 fu­els like methane and precursors like formic acid or syngas, as well as C1+ com­pounds like ac­etate, 2-oxybut­yrate, bu­tyrate, ethanol, and butanol. At the same time, BES inte­grate well into urban in­frastructure without the need for arable land. However, except for meth­ane, none of these fuels are readily com­bustible in their pure form. While elec­tromethane is a com­mercially avail­able al­ternative to fossil natu­ral gas, its volumetric energy den­sity of 40-80 MJ/m3 is lower than that of gasoline with 35-45 GJ/m3. This, the necessary technical modifications, and the psychological barrier of tanking a gaseous fuel make methane hard to sell to automobilists. To pro­duce liq­uid fuel, carbon chains need to be elongated with al­cohols or better, hy­drocarbons as fi­nal prod­ucts. To this end, syngas (CO + H2) is theoreti­cally a viable option in the Fischer-Tropsch process. In reality, syngas pre­cursors are ei­ther fossil fu­els (e.g. coal, natural gas, methanol) or biomass. While the for­mer is ob­viously not CO2-neu­tral, the latter com­petes for arable land. The di­rect con­version of CO2 and electrolytic H2 to C1+ fuels, in turn, is catalyzed out by elec­troactive microbes in the dark (see title figure), avoid­ing food crop com­petition for sun-lit land. Unfortunately, little re­search has been under­taken beyond proof of con­cept of few electroactive strains. In stark con­trast, a plethora of metabolic studies in non-BES is avail­able. These studies often pro­pose the use of GMOs or complex or­ganic sub­strates as precur­sors. We propose to systemati­cally identify metabolic strategies for liquid bio-electrically engineered fuel (BEEF) production. The fastest approach should start by screening meta­bolic data­bases using es­tablished methods of metabolic modeling, fol­lowed by high throughput hypothesis testing in BES. Since H2 is the intermediate in bio-electrosynthesis, the most efficient strategy is to focus on CO2 and H2 as di­rect pre­cursors with as few in­termediate steps as pos­sible. Scala­bility and energy effi­ciency, eco­nomic feasibil­ity that is, are pivotal elements.

First, an electrotrophic acetogen produces acetate, which then used by heterotrophic algae in a consecutive step.

The biggest obstacle for BEEF production is lacking knowledge about pathways that use CO2 and electrolytic H2. This gap exists despite metabolic data­bases like KEGG and more recently KBase, making metabolic design and adequate BEEF strain selection a guessing game rather than an educated ap­proach. Nonetheless, metabolic tools were used to model fuel pro­duction in single cell yeasts and various prokaryotes. In spite of their shortcomings, metabolic data­bases were also employed to model species interactions, for example in a photo-het­erotroph consor­tium using software like ModelSEED / KBase (http://mod­elseed.org/), RAVEN / KEGG and COBRA. A first sys­tematic at­tempt for BEEF cul­tures produci­ng acetate demonstrated the usability of KBase for BES. This research was a bottom-up study which mapped ex­isting genomes onto existing BEEF consor­tia. The same tool can also be em­ployed in a top-down ap­proach, starting with the desired fuel to find the re­quired or­ganisms. Some possi­ble BEEF organisms are the following.

Possible pathways for BEEF production involving Clostridium, 3, or heterotrophic phototrophs, 7, further processing by yeasts

Yeasts are among the microorganisms with the greatest potential for liquid biofuel production. Baker’s yeast, (Saccha­romyces cerevisiae) is the most promi­nent exam­ple. While known for ethanol fermentat­ion, yeasts also produce fusel oils such as bu­tane, phenyl, and amyl derivate aldehy­des and alco­hols. Unlike ethanol, which is formed via sugar fer­mentation, fusel oil is syn­thesized in branched-off amino acid pathways followed by alde­hyde reduction. Many en­zymes involved in the re­duction of aldehydes have been identified, with al­cohol dehydro­genases be­ing the most commonly ob­served. The corre­sponding reduc­tion reactions require reduced NADH⁠ but it is not known whether H2 pro­duced on cathodes of BES can be in­volved.
Clostridia, for example Clostridium acetobutylicum and C. carboxidivo­rans, can pro­duce alcohols like butanol, isopropanol, hexanol, and ketones like acetone from complex sub­strates (starch, whey, cel­lulose, etc. ) or from syngas. Clostridial me­tabolism has been clarified some time ago and is dif­ferent from yeast. It does not necessar­ily require com­plex precursors for NAD+ reduction and it was shown that H2, CO, and cath­odes can donate elec­trons for alcohol production. CO2 and H2 were used in a GMO clostridium to produce high titers of isobu­tanol. Typi­cal representa­tives for acetate produc­tion from CO2 and H2 are C. ljungdahlii, C. aceticum, and Butyribac­terium methy­lotrophicum. Sporo­musa sphaeroides pro­duces acetate in BES. Clostridia also dominated mixed cul­ture BESs converting CO2 to butyrate. They are therefore prime targets for low cost biofuel production. Alcohols in clostridia are produced from acetyl-CoA. This reaction is re­versible, al­lowing ac­etate to serve as substrate for biofuel production with extra­cellular en­ergy sup­ply. Then, en­ergy con­servation, ATP syn­thesis that is, can be achieved from ethanol electron bifurca­tion or H2 oxida­tion via respi­ration. While pos­sible in anaero­bic clostridia, it is hitherto unknown whether elec­tron bifurca­tion or res­piration are linked to alcohols or ke­tone synthesis.
Phototrophs like Botryococcus produce C1+ biofuels as well. They synthesize a number of different hydro­carbons including high value alkanes and alkenes as well as terpenes. However, high titers were achieved by only means of ge­netic engineering, which is economically not feasible in many countries due to regulatory constrains. Moreover, aldehyde dehy­dration/deformylation to alkanes or alkenes requires molecular oxygen to be present. Also the olefin path­way of Syne­chococcus depends on molecular oxygen with the cytochrome P450 involved in fatty acid de­carboxylation. The presence of molecular oxygen affects BES performance due to immediate product degrada­tion and unwanted cathodic oxygen reduction. In contrast, our own preliminary experi­ments (see title photo) and a corrosion experi­ment show that algae can live in the dark using electrons from a cath­ode. While the en­zymes in­volved in the production of some algal biofuels are known (such as olefin and alde­hyde de­formylation), it is not known whether these pathways are connected to H2 utilization (perhaps via ferredox­ins). Such a con­nection would be a promising indicator for the possibility of growing hydrocar­bon produc­ing cyanobacteria on cathodes of BES and should be examined in future research.
At Frontis Energy we believe that a number of other microorganisms show potential for BEEF production and these deserve further investi­gation. To avoid GMOs, BES compatible co-cultures must be identified via in silico meta­bolic reconstruc­tion from existing databases. Possible inter-species intermediates are unknown but are prerequisite for suc­cessful BES operation. Finally, a techno-economical assessment of BEEF pro­duction, with and with­out car­bon taxes, and compared with chemical methods, will direct future research.