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Unlocking the Potential of Conducting Polymers for Sustainable Water Treatment and Energy Solutions

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.

Image: Pixabay

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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.

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Poly-electrolyte layers determine the efficiency of desalination membranes

Increasing water scarcity and pollution with micropollutants are responsible for the increasing cost of drinking water. Desalination of sea water and better wastewater treatment are necessary to counter this trend. Membranes can desalinate and remove most wastewater pollution. However, a lot of energy is required. Therefore, modern membranes must be more efficient in order to achieve satisfactory results.

Nano-filtration membranes consisting of poly-electrolytic layers are a promising approach to treat water more efficiently. Accordingly, the composition of poly-electrolytic layers has stirred up much interest in the production of nano-filtration membranes. Such membranes are manufactured layer by layer, which enables a good tuning of membrane properties for different purposes.

Commercially available nano-filtration membranes are usually a trade-off between high water permeability and good salt retention (desalination). This trade-off impacts either the quality or the volume of the cleaned water. Nano-filtration membranes that are produced in layer by layer can have a positive impact on this trade-off balance due to the formation of nano scaled layers. It is important to know which component plays a crucial role in the layer forming process.

A research group of the Technical University Eindhoven in the Netherlands had therefore undertaken the task of examining these layer components more closely. They specifically investigated the poly-electrolyte concentration. It is known that a higher poly-electrolyte concentration produces thicker layers. However, their impact on the membrane performance has so far been unknown. They now published their work, in which the researchers used two well-known strong poly-electrolytes: PDADMAC and PSS (polydiallyldimethylammonium chloride and poly(sodium-4-styrene sulfonate)). The membrane output was examined with regard to water permeability, the molecular weight cutoff and salt retention.

In the first double layer, the membranes made with a 50 mM saline solution showed a lower water permeability and molecular weight cutoff, as well as better salt retention (magnesium sulfate) due to the higher poly-electrolyt concentration. After a certain number of double layers, the molecular weight cutoff and the salt retention efficiency for all poly-electrolyte concentration leveled off. The higher the poly-electrolyte concentration, the sooner the plateau value was reached.

The membranes prepared with a 1 M salt concentration had a lower or comparable salt retention efficiency with one exception. The scientists concluded that the poly-electrolyte concentration significantly changed the membrane properties. A plateau was reached with seven or more double layers. The thicker layers showed a lower water permeability than those that were coated with poly-electrolyte solutions using a 50 mM salt concentration. Due to the reduced swelling of these membranes, they all had better salt retention efficiency, with the exception of magnesium chloride.

The results showed that increasing the poly-electrolyte concentration also increased the amount of poly-electrolyte adsorption. Due to a higher coating thickness, this led to lower permeability with pure water. However, this did not lead to a lower molecular weight cutoff or salt retention. The additional poly-electrolyte adsorption resulted in fewer links between the individual layers. The higher diffusivity of PDADMAC compared to PSS resulted in highly positively charged membranes, which in turn led to a better salt retention of magnesium and sodium chloride.

Overall, increased poly-electrolyte concentration and the salt concentration influenced the membrane charge exclusion significantly due to a higher charged surface, which led to better salt retention. However, the membrane size exclusion has not changed, which led to the same plateau values. The study presented here will allow chemists to produce better tuned desalination membranes, which will reduce the energy requirement and raw material requirements during production.

Image: Shutterstock

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Alternating catholyte flow improves microbial electrosynthesis start-up

Microbial electrolysis is a technology that uses living microorganisms as electro-catalysts in electrolysis cells. The technology can be used for wastewater treatment. Earlier, we proposed that microbial electrolysis be used to decentralize wastewater treatment and biogas production. Since this is a process that converts CO2 into organic compounds using electricity it can also be used for CO2 valorization. Besides methane, such electrolysis cells produce compounds such as acetic acid (vinegar), caproic acid, and others. It is then called microbial electrosynthesis.

However, the main problem with microbial electrolysis and electrosynthesis is the long start-up time. The start-up time is the time required for the microorganisms to form a biofilm on the electrode surface and to start producing the desired products. It can range from several weeks to several months, depending on the operating conditions and the type of microorganisms. This long start-up time limits the feasibility and the scalability of microbial electrosynthesis, as well as its economic and environmental benefits.

Now, scientists of the Wageningen University in the Netherlands presented new research, which aimed to reduce the start-up time of microbial electrosynthesis. By using a novel technique that involves alternating the direction of the catholyte flow through a three-dimensional electrode they were able to reduce the startup time to only ten days. They hypothesized that this technique enhances mass transfer and biofilm formation, and thus accelerates the CO2 reduction and the product formation. This was a start-up time reduction of 50%, compared to a conventional flow-through electrode.

 

The alternating electrolyte flow also reduced the power consumption to 136 kWh per kg of hydrogen. After 60 days, the local hydrogen concentration at the cathode was at a maximum of 600 μM, which indicates a better mass transport and thus a more active biofilm. The researchers speculated that the alternating catholyte flow improved mass transport, because the hydrogen could be better distributed over the cathode layers. In addition, the researchers think that alternating the flow refreshed potential “dead zones” in the cathode chamber.

The pH in the catholyte was 5.8–6.8 and in optimal range for electrosynthetic microorganisms. Production of short and medium chain fatty acids was linked to the presence of microorganisms identified as Peptococcaceae and Clostridium sensu stricto 12 species. Hydrogenotrophic methanogenesis was also observed and was linked to Methanobrevibacter. The latter is a typical constituent of microbial electrolysis cells that use higher intermediate hydrogen concentrations for electrosynthesis at the cathode.

However, there are limitations of the technique, such as the energy efficiency, the product selectivity, and the scalability of microbial electrosynthesis. Such limitations are typical for bench top experiments. We are therefore looking forward to see an industrial application of this new method.

 

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Trace metals accelerate hydrogen evolution reaction of biocathodes in microbial electrolysis cells

It has been known that microbial biofilms on biocathodes improve the productions rates of hydrogen evolution reaction (HER). This is the process of producing hydrogen gas from water using electricity. The hydrogen evolution was even accelerated when the biofilm colonizing a biocathode was killed. Different types of bacteria, such as exoelectrogenic (Geobacter sulfurreducens), non-exoelectrogenic (Escherichia coli), and a hydrogenotrophic methanogen (Methanosarcina barkeri) accomplished the feat but Geobacter was the fastest. Even cell debris and metalloproteins catalyzed HER. Therefore, living cells are not required for enhanced HER, and biocathodes could be a cheap and environmentally friendly alternative to precious metal catalysts. While the authors back then speculated on the role of metalloproteins, a new publication in Electrochimica Acta by researchers of Wageningen University shows that indeed trace metals in the growth medium are responsible for the observed rate acceleration.

The authors used a mixture of metal compounds present in the microbial medium such as cobalt, copper, iron, manganese, molybdenum, nickel and zinc salts as well as the metal chelating agent ethylenediaminetetraacetic acid (EDTA) as the catalyst for the HER under microbial compatible conditions (near-neutral pH, mesophilic temperature, aquous electrolyte).

They performed a series of experiments to investigate the effect of different parameters on the catalytic activity and stability of the trace metal mix medium. These parameters included the concentration of the metal compounds, the presence or absence of EDTA, the type of electrode material, and the type of electrolyte. Various techniques to measure the cathodic current, the hydrogen production rate, the overpotential, and the exchange current density of the HER were used.

The results show that the trace metal mix medium increased the cathodic current and the electron recovery into hydrogen significantly, and that copper and molybdenum were the most active compounds in the mix. This is surprising because the previous publication found mostly cobalt and iron compounds on the surface of the biocathodes. Both of which are good hydrogen catalysts as well, whereas molybdenum sulfide for example, did not increase production rates in methanogenic microbial electrolysis cells. HER is the rate determining reaction in methanogenic electrolysis cells because it is the intermediate:

4 H2 + CO2 → CH4 + 2 H2O

The results also showed that removing EDTA from the mix improved the catalyst performance further, as EDTA acted as a complexing (chelating) agent that reduced the availability of metal ions for HER. The results also showed that carbon-based electrodes were more suitable than metal-based electrodes for HER, possibly because they have a higher surface area. This is an interesting result because it was previously thought that the mechanism behind the better performance of carbon electrodes was the microbial preference to adhere to carbon than to metal surfaces. The results also showed that using microbial growth medium as the electrolyte did not affect the catalyst performance significantly, as compared to using phosphate buffer solution.

The authors concluded that their method was a simple, cheap, and environmentally friendly way to prepare effective catalysts for HER using trace metals from microbial growth media. They suggested that these catalysts could be integrated in biological systems for in situ hydrogen production in bio-electrochemical and fermentation processes. Indeed, it is inevitable not to use trace metals in microbial electrolysis cells as they are essential to sustain growth.

Both articles demonstrate that trace metals can play an important role in the HER, and that they can be derived from biological sources. However, they also have some limitations and challenges, such as the stability, selectivity, and scalability of the catalysts. Therefore, further research is needed to optimize the performance and applicability of trace metal-based catalysts for HER.

(Image: US National Science Foundation)

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Bio-electric systems help PFAS removal

Per- and polyfluoroalkyl substances (PFAS) have been manufactured for various applications for many decades. These include medical applications, such as implants and catheters, or consumer products for firefighting, plastics, cookware, and cosmetics. Likewise, PFAS are required in countless industrial applications, such as in the automotive industry, the chemical industry and the energy sector, including hydrogen electrolysis and fuel cells (e.g. Nafion™). They help apparatuses to function properly, reduce wear and the risk of accidents. The widespread use of PFAS has led to traces of these substances entering the environment worldwide. Typical sites with higher environmental PFAS concentrations include airports, chemical plants, fire brigades, military facilities etc.

The long-term health effects of these substances are currently a matter of controversy, particularly with regard to their chemical stability (a desired property).

In addition to completely avoiding their entry into the environment, PFAS can also be eliminated from it. For example, activated charcoal is often used to adsorb PFAs onto it. However, this method is not efficient in soils. Ideally, the activated carbon itself would have to be further processed in order to reuse PFAS. This process is very energy intensive.

As for many treatment processes, microbes can be used also for PFAS. Such biological methods are called bioremediation. However, the carbon-fluorine (C-F) bonds in PFAS are among the strongest covalent bonds in organic chemistry. In addition, there are very few naturally occurring C-F bonds in nature. They only occur in small concentrations. A prominent example is fluoroacetic acid, a highly toxic compound produced by the South African poisonous gifblaar. Few microorganisms with the ability to break the C-F bond have been identified. Thus, bioremediation of PFAS is possible but a slow process.

As already described in our previous articles, bio-electrical systems can accelerate microbial conversion processes. With bio-electrical systems it is possible to offer microbes a greater electrochemical potential gradient. Since this leads to larger energy gain in microbial metabolism, such metabolic rates can be accelerated. This process is successfully employed to clean industrial waste water.

In bio-electrical systems, microorganisms along with contaminants are placed in an electrochemical apparatus. The electrodes of such a system serve as electron donors or acceptors. The biodegradation is can be measured via the electric current.

Indeed, bio-electric systems have been used to degrade fluorinated alkanes. For example, the anti-inflammatory drug dexamethasone was successfully eliminated using such an apparatus. As proposed for bio-electrical liquid fuel, designer microbiomes could also be studied for PFAS. Other drug residues, such as Prozac™, should also be examined to ensure absence from the environment.

At Frontis Energy we are looking forward to new developments for PFAS removal in bio-electrical systems.

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Decentralized waste energy systems produce biogas where it is needed

Among others, the current European energy crisis was caused by a surge in demand after the pandemic, the embargo on Russia, the reluctance of investors to finance fossil energy projects and the throttling of production by the OPEC countries. In this complex situation, European countries are forced to develop alternatives and renewable energy sources. At the same time, however, natural gas is difficult to replace in many industries. One exception is the food and beverage industry, which sits enormous untapped resources of biogas in their wastewater.

Wastewater is a resource of which 380 billion m³ are produced worldwide. It contains valuable nutrients and energy. Global production is projected to increase by 51% by 2050. Wastewater treatment consumes about 3-4% of the energy generated globally. The full reeovery of the energy that is contained in this wastewater would completely offset the energy consumption of its treatment and in many cases even produce a surplus. In addition, the entire global water treatment is estimated to account for up to 5% of man-made CO2 production. Unfortunately, many businesses and municipalities do not invest in complex and expensive wastewater treatment technologies and continue to waste this valuable resource. The European Biogas Association estimates that by 2050, a maximum of 65% of gas requirements (~167 billion m³) could be covered by biogas.

Europe is the largest cheese maker in the world. More than 9 million tons of cheese are produced annually. With every ton of cheese, 9 m³ of cheese whey remain. Despite its high nutritional value, whey is often treated like wastewater for various reasons. Yet, the very high organic load in the whey makes it difficult to treat. Wasted whey can also be used for biogas production. In addition to whey, regular wastewater is also produced by cheese makers. For example, a medium-sized cheese factory pays 1.5 million euros a year for its waste water. Reducing these costs by producing biogas would turn dairy industry wastewater into a valuable resource.

This situation is similar in many other food and beverage sectors such as breweries, distilleries, winemakers, bakeries etc. All of these sectors have high energy requirements. Renewable electrical energy cannot meet this need. The market for wastewater treatment in Europe and the US is around 12 billion euros.

Traditional wastewater treatment is a cascaded process including aeration and anaerobic sludge digestion followed by incineration. These methods often consume more than 70% of the energy in a wastewater treatment plant. If contaminants such as high-energy total organic carbon or ammonia were converted into biogas before the process, at least 80% of the energy needed for wastewater treatment could be saved. It is absurd that this energy is removed from the wastewater using even more energy.

An ever-increasing number of sewage treatment plants already recover the resources contained in their wastewater, apart from the water itself. The oldest recivered products are biogas and fertilizers made from sewage sludge. Due to its heavy metal content such as copper and mercury, sewage sludge is no longer used as fertilizer but incinerated.

Biogas is particularly popular in Europe as the produced volumes and prices are high enough to compete with natural gas. Biogas is also a green alternative to natural gas as no additional CO2 is emitted. (Hence, it is often called Renewable Natural Gas in North America.) A disadvantage of classic biogas is the CO2 and sulfide content. Another disadvantage is that anaerobic digestion is the terminal treatment step, wasting valuable wastewater resources in the preceding treatment. Finally, the size and complexity of current digestion requires significant commitment from users when it comes to capital expenditures. Most food manufacturers prefer to focus on making food rather than cleaning their wastewater.

Novel high-performance biogas reactors solve these problems through miniaturization. A 20-fold size reduction is achieved compared to conventional systems. The new technology used was developed in Japan in the early 1990s and is called microbial electrolysis. The electrolysis of wastewater is catalyzed by electroactive microorganisms on the anode (the positive electrode). The reaction products are CO2 (from organic matter) and nitrogen gas (N2 from ammonia).

Principle of a microbial electrolysis reactor. On the left anode, the organic material is oxidized to CO2. The free electrons are absorbed by the anode and transported to the cathode. Hydrogen gas (H2) is released there. CO2 and hydrogen form methane, the final microbial reaction product.

At the same time, hydrogen gas (H2) is generated at the cathode (the negative electrode). This hydrogen reacts with CO2 to form methane. The final methanation step completes the biocatalytic treatment of the wastewater. Gas grid injection is one possible use. But for cheese makers, the gas would be used on site to generate electricity and/or heat.

The reaction is accelerated using an applied voltage and is based on the laws of thermodynamics. As a result, the reactor volume can be reduced. The size reduction has several advantages. First, it makes biogas accessible in markets where it was previously not possible due to the high investment costs. Second, it enables higher throughput at a lower cost. Smaller units are mobile and can be shared, moved or rented. After all, food manufacturers want to do what they do best, which is to make food.

 

Image: Pixabay

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Nanostructured membranes improve the gas separation of carbon dioxide

To reduce greenhouse gas emissions, various technologies are in development requiring the separation of mixed gases, such as  CO2 and methane or CO2 and nitrogen gas (CO2/CH4 and CO2/N2). Compared to other separation technologies, polymer membranes are  good candidates for industrial use. This is due to their low operating costs, high energy efficiency and simple scalability.

The gas permeability and selectivity, as well as the cost of these polymer membranes are the crucial criteria for their industrial use. These criteria are influenced by molecular order processes during polymerization at nano- and micrometer levels. However, the processes regulating the molecular order of most common membranes do not occur on these levels. Hence, there is little control over them during manufacturing. Not much is known about materials with self organizing properties and their influence on molecular order and gas separation.

Chemists at the Technical University of Eindhoven in the Netherlands examined the effects of the layer distance within the membrane and its halogenation on the gastrunge and published their results in the MDPI Membranes journal. They focused on the separation of helium, CO2 and nitrogen. The researchers used liquid crystal membranes for their investigation. Liquid crystal molecules can align in various nanostructures. These structures vary depending on the manufacturing process and can therefore be controlled. As a result, liquid crystal membranes are ideal in order to investigate the influence of nanostructures on gas separation.

A frequently used manufacturing method is to commence the self organization of the reactive liquid crystal molecules in a cell with spacers. This helps to better control the membrane thickness and alignment and ultimately control the molecular orientation. The final network of the liquid crystal molecules and their fixation in nanostructures is required to achieve mechanical strength. For example, high ordered crystal membranes (i.e. not liquid crystals) have a lower gas permeability. Nonetheless, they also are characterized by a higher selectivity for helium and CO2 compared to nitrogen.

A lamellar morphology and the flow direction of the gas also have a great influence on selectivity and permeability of the membrane. It is also known that halogen atoms such as chlorine or fluorine improve CO2 permeability and selectivity by affecting both gas solubility and diffusion.

In the presented experiments, all liquid crystal membranes with similar chemical compositions, but different halogenated alkyl chains, were aligned. The CO2 sorption and the entire gas permeation were better if their layers were further apart. The gas solubility itself had no impact. This was confirmed by the increased gas diffusion coefficients, which were also determined in the experiments.

Bulky halogens had only limited influence on gas permeability and selectivity. The CO2 permeability of all halogenated liquid crystal membranes increased due to a slightly higher CO2 solubility and diffusion coefficients, which led to improved selectivity for CO2. The layer distance in particular was a crucial factor that directly influenced the diffusion coefficient. The researchers recommended that future investigations should focus on improving separation performance, for example by reducing the membrane thickness.

At Frontis Energy, we are looking forward to a good commercial product that can separate CO2 from gas mixtures, such as biogas, effectively and cheap.

Photo: Pixabay / SD-Pictures