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New catalyst unveils the hidden power of water for green hydrogen generation
Hydrogen is a promising chemical and energy vector to decarbonize our society. Unlike conventional fuels, hydrogen utilization as a fuel does not generate carbon dioxide in return. Unfortunately, today, most of the hydrogen that is produced in our society comes from methane, a fossil fuel. It does so in a process (methane reforming) that leads to substantial carbon dioxide emissions. Therefore, the production of green hydrogen requires scalable alternatives to this process.
To date, water electrolysis, and in particular PEM, has required catalysts based on scarce, rare elements, such as platinum and iridium, among others. Only a few compounds combine the required activity and stability at the harsh chemical environment imposed by this reaction. This is specially challenging in the case of anode catalysts, which have to operate at highly corrosive acidic environments — conditions where only iridium oxides have shown stable operation at the required industrial conditions. But iridium is one of the scarcest elements on earth.
In search for possible solutions, a team of scientists has recently taken an important step to find alternatives to iridium catalysts. This multidisciplinary team has managed to develop a novel way to confer activity and stability to an iridium-free catalyst by harnessing so far unexplored properties of water. The new catalyst achieves, for the first time, stability in PEM water electrolysis at industrial conditions without the use of iridium.
This breakthrough, published in Science, has been carried out by ICFO researchers Ranit Ram, Dr. Lu Xia, Dr. Anku Guha, Dr. Viktoria Golovanova, Dr. Marinos Dimitropoulos, Aparna M. Das and Adrián Pinilla-Sánchez, and led by Professor at ICFO Dr. F. Pelayo García de Arquer; and includes important collaborations from the Institute of Chemical Research of Catalonia (ICIQ), The Catalan Institute of Science and Technology (ICN2), French National Center for Scientific Research (CNRS), Diamond Light Source, and the Institute of Advanced Materials (INAM).
Dealing with the acidity
Combining activity and stability in highly acidic environment is challenging. Metals from the catalyst tend to dissolve, as most materials are not thermodynamically stable at low pH and applied potential, in a water environment. Iridium oxides combine activity and stability at these harsh conditions, and that is why they are the prevalent choice for anodes in proton-exchange water electrolysis.
The search for alternatives to iridium is not only an important applied challenge, but a fundamental one. Intense research on the look for non-iridium catalysts has led to new insights on the reaction mechanisms and degradation, especially with the use of probes that could study the catalysts during operation combined with computational models. These led to promising results using manganese and cobalt oxide-based materials, and exploiting different structures, composition, and dopants, to modify the physicochemical properties of the catalysts.
While insightful, most of these studies were performed in fundamental not-scalable reactors and operating at softer conditions that are far from the final application, especially in terms of current density. Demonstrating activity and stability with non-iridium catalysts in PEM reactors and at PEM-relevant operating conditions (high current density) had to date remained elusive.
To overcome this, the ICFO, ICIQ, ICN2, CNRS, Diamond Light Source and INAM researchers came up with a new approach in the design of non-iridium catalysts, achieving activity and stability in acid media. Their strategy, based on cobalt (very abundant and cheap), was quite different to the common paths.
“Conventional catalyst design typically focuses on changing the composition or the structure of the employed materials. Here, we took a different approach. We designed a new material that actively involves the ingredients of the reaction (water and its fragments) in its structure. We found that the incorporation of water and water fragments into the catalyst structure can be tailored to shield the catalyst at these challenging conditions, thus enabling stable operation at the high current densities that are relevant for industrial applications,” explains Professor at ICFO, García de Arquer. With their technique, consisting in a delamination process that exchanges part of the material by water, the resulting catalyst present as a viable alternative to iridium-based catalysts.
A new approach: the delamination process
To obtain the catalyst, the team looked into a particular cobalt oxide: cobalt-tungsten oxide (CoWO4), or in short CWO. On this starting material, they designed a delamination process using basic water solutions whereby tungsten oxides (WO42-) would be removed from the lattice and exchanged by water (H2O) and hydroxyl (OH–) groups in a basic environment. This process could be tuned to incorporate different amount of H2O and OH– into the catalyst, which would then be incorporated onto the anode electrodes.
The team combined different photon-based spectroscopies to understand this new class of material during operation. Using infrared Raman and x-rays, among others, they were able to assess the presence of trapped water and hydroxyl groups, and to obtain insights on their role conferring activity and stability for water splitting in acid. “Being able to detect the trapped water was really challenging for us,” continues leading co-author Dr. Anku Guha. “Using Raman spectroscopy and other light-based techniques we finally saw that there was water in the sample. But it was not “free” water, it was confined water”; something that had a profound impact on performance.
From these insights, they started working closely with collaborators experts in catalyst modelling. “The modeling of activated materials is challenging as large structural rearrangments take place. In this case the delamination employed in the activation treatment increases the number of active sites and changes the reaction mechanism rendering the material more active. Understanding these materials requires a detailed mapping between experimental observations and simulations,” says Prof. Núria López from ICIQ. Their calculations, led by a leading co-author Dr. Hind Benzidi, were crucial to understand how the delaminated materials, shielded by water, were not only thermodynamically protected against dissolution in highly acidic environments, but also active.
But, how is this possible? Basically, the removal of tungsten-oxide leaves a hole behind, exactly where it was previously located. Here is where the “magic” happens: water and hydroxide, which are vastly present in the medium, spontaneously fill the gap. This in turn shields the sample, as it renders the cobalt dissolution an unfavorable process, effectively holding the catalyst components together.
Then, they assembled the delaminated catalyst into a PEM reactor. The initial performance was truly remarkable, achieving higher activity and stability than any prior art. “We increased five times the current density, arriving to 1 A/cm2 — a very challenging landmark in the field. But, the key is, that we also reached more than 600 hours of stability at such high density. So, we have reached the highest current density and also the highest stability for non-iridium catalysts,” shares leading co-author Dr. Lu Xia.
“At the beginning of the project, we were intrigued about the potential role of water itself as the elephant in the room in water electrolysis,” explains Ranit Ram, first author of the study and instigator of the initial idea. “No one before had actively tailored water and interfacial water in this way.” In the end, it turned out to be a real game changer.
Even though the stability time is still far from the current industrial PEMs, this represents a big step towards making them not dependent on iridium or similar elements. In particular, their work brings new insights for water electrolysis PEMs design, as it highlights the potential to address catalyst engineering from another perspective; by actively exploiting the properties of water.
Towards the industrialization
The team has seen such potential in the technique that they have already applied for a patent, with the aim of scaling it up to industry levels of production. Yet, they are aware of the non-triviality of taking this step, as Prof. García de Arquer notices: “Cobalt, being more abundant than iridium, is still a very troubling material considering from where it is obtained. That is why we are working on alternatives based on manganese, nickel and many other materials. We will go through the whole the periodic table, if necessary. And we are going to explore and try with them this new strategy to design catalysts that we have reported in our study.”
Despite the new challenges that will for sure arise, the team is convinced of the potential of this delamination process and they are all determined to pursue this goal. Ram, in particular, shares: “I have actually always wanted to advance renewable energies, because it will help us as a human community to fight against climate change. I believe our studies contributed one small step into the right direction.”
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Early dark energy could resolve cosmology’s two biggest puzzles
A new study by MIT physicists proposes that a mysterious force known as early dark energy could solve two of the biggest puzzles in cosmology and fill in some major gaps in our understanding of how the early universe evolved.
Now, the MIT team has found that both puzzles could be resolved if the early universe had one extra, fleeting ingredient: early dark energy. Dark energy is an unknown form of energy that physicists suspect is driving the expansion of the universe today. Early dark energy is a similar, hypothetical phenomenon that may have made only a brief appearance, influencing the expansion of the universe in its first moments before disappearing entirely.
Some physicists have suspected that early dark energy could be the key to solving the Hubble tension, as the mysterious force could accelerate the early expansion of the universe by an amount that would resolve the measurement mismatch.
The MIT researchers have now found that early dark energy could also explain the baffling number of bright galaxies that astronomers have observed in the early universe. In their new study, reported in the Monthly Notices of the Royal Astronomical Society, the team modeled the formation of galaxies in the universe’s first few hundred million years. When they incorporated a dark energy component only in that earliest sliver of time, they found the number of galaxies that arose from the primordial environment bloomed to fit astronomers’ observations.
“You have these two looming open-ended puzzles,” says study co-author Rohan Naidu, a postdoc in MIT’s Kavli Institute for Astrophysics and Space Research. “We find that in fact, early dark energy is a very elegant and sparse solution to two of the most pressing problems in cosmology.”
The study’s co-authors include lead author and Kavli postdoc Xuejian (Jacob) Shen, and MIT professor of physics Mark Vogelsberger, along with Michael Boylan-Kolchin at the University of Texas at Austin, and Sandro Tacchella at the University of Cambridge.
Big city lights
Based on standard cosmological and galaxy formation models, the universe should have taken its time spinning up the first galaxies. It would have taken billions of years for primordial gas to coalesce into galaxies as large and bright as the Milky Way.
But in 2023, NASA’s James Webb Space Telescope (JWST) made a startling observation. With an ability to peer farther back in time than any observatory to date, the telescope uncovered a surprising number of bright galaxies as large as the modern Milky Way within the first 500 million years, when the universe was just 3 percent of its current age.
“The bright galaxies that JWST saw would be like seeing a clustering of lights around big cities, whereas theory predicts something like the light around more rural settings like Yellowstone National Park,” Shen says. “And we don’t expect that clustering of light so early on.”
For physicists, the observations imply that there is either something fundamentally wrong with the physics underlying the models or a missing ingredient in the early universe that scientists have not accounted for. The MIT team explored the possibility of the latter, and whether the missing ingredient might be early dark energy.
Physicists have proposed that early dark energy is a sort of antigravitational force that is turned on only at very early times. This force would counteract gravity’s inward pull and accelerate the early expansion of the universe, in a way that would resolve the mismatch in measurements. Early dark energy, therefore, is considered the most likely solution to the Hubble tension.
Galaxy skeleton
The MIT team explored whether early dark energy could also be the key to explaining the unexpected population of large, bright galaxies detected by JWST. In their new study, the physicists considered how early dark energy might affect the early structure of the universe that gave rise to the first galaxies. They focused on the formation of dark matter halos — regions of space where gravity happens to be stronger, and where matter begins to accumulate.
“We believe that dark matter halos are the invisible skeleton of the universe,” Shen explains. “Dark matter structures form first, and then galaxies form within these structures. So, we expect the number of bright galaxies should be proportional to the number of big dark matter halos.”
The team developed an empirical framework for early galaxy formation, which predicts the number, luminosity, and size of galaxies that should form in the early universe, given some measures of “cosmological parameters.” Cosmological parameters are the basic ingredients, or mathematical terms, that describe the evolution of the universe.
Physicists have determined that there are at least six main cosmological parameters, one of which is the Hubble constant — a term that describes the universe’s rate of expansion. Other parameters describe density fluctuations in the primordial soup, immediately after the Big Bang, from which dark matter halos eventually form.
The MIT team reasoned that if early dark energy affects the universe’s early expansion rate, in a way that resolves the Hubble tension, then it could affect the balance of the other cosmological parameters, in a way that might increase the number of bright galaxies that appear at early times. To test their theory, they incorporated a model of early dark energy (the same one that happens to resolve the Hubble tension) into an empirical galaxy formation framework to see how the earliest dark matter structures evolve and give rise to the first galaxies.
“What we show is, the skeletal structure of the early universe is altered in a subtle way where the amplitude of fluctuations goes up, and you get bigger halos, and brighter galaxies that are in place at earlier times, more so than in our more vanilla models,” Naidu says. “It means things were more abundant, and more clustered in the early universe.”
“A priori, I would not have expected the abundance of JWST’s early bright galaxies to have anything to do with early dark energy, but their observation that EDE pushes cosmological parameters in a direction that boosts the early-galaxy abundance is interesting,” says Marc Kamionkowski, professor of theoretical physics at Johns Hopkins University, who was not involved with the study. “I think more work will need to be done to establish a link between early galaxies and EDE, but regardless of how things turn out, it’s a clever — and hopefully ultimately fruitful — thing to try.”
“We demonstrated the potential of early dark energy as a unified solution to the two major issues faced by cosmology. This might be an evidence for its existence if the observational findings of JWST get further consolidated,” Vogelsberger concludes. “In the future, we can incorporate this into large cosmological simulations to see what detailed predictions we get.”
This research was supported, in part, by NASA and the National Science Foundation.
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Plant-derived secondary organic aerosols can act as mediators of plant-plant interactions
A new study published in Science reveals that plant-derived secondary organic aerosols (SOAs) can act as mediators of plant-plant interactions. This research was conducted through the cooperation of chemical ecologists, plant ecophysiologists and atmospheric physicists at the University of Eastern Finland.
The study showed that Scots pine seedlings, when damaged by large pine weevils, release VOCs that activate defences in nearby plants of the same species. Interestingly, the biological activity persisted after VOCs were oxidized to form SOAs. The results indicated that the elemental composition and quantity of SOAs likely determines their biological functions.
“A key novelty of the study is the finding that plants adopt subtly different defence strategies when receiving signals as VOCs or as SOAs, yet they exhibit similar degrees of resistance to herbivore feeding,” said Professor James Blande, head of the Environmental Ecology Research Group. This observation opens up the possibility that plants have sophisticated sensing systems that enable them to tailor their defences to information derived from different types of chemical cue.
“Considering the formation rate of SOAs from their precursor VOCs, their longer lifetime compared to VOCs, and the atmospheric air mass transport, we expect that the ecologically effective distance for interactions mediated by SOAs is longer than that for plant interactions mediated by VOCs,” said Professor Annele Virtanen, head of the Aerosol Physics Research Group. This could be interpreted as plants being able to detect cues representing close versus distant threats from herbivores.
The study is expected to open up a whole new complex research area to environmental ecologists and their collaborators, which could lead to new insights on the chemical cues structuring interactions between plants.
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Folded or cut, this lithium-sulfur battery keeps going
Most rechargeable batteries that power portable devices, such as toys, handheld vacuums and e-bikes, use lithium-ion technology. But these batteries can have short lifetimes and may catch fire when damaged. To address stability and safety issues, researchers reporting in ACS Energy Letters have designed a lithium-sulfur (Li-S) battery that features an improved iron sulfide cathode. One prototype remains highly stable over 300 charge-discharge cycles, and another provides power even after being folded or cut.
The team coated iron sulfide cathodes in different polymers and found in initial electrochemical performance tests that polyacrylic acid (PAA) performed best, retaining the electrode’s discharge capacity after 300 charge-discharge cycles. Next, the researchers incorporated a PAA-coated iron sulfide cathode into a prototype battery design, which also included a carbonate-based electrolyte, a lithium metal foil as an ion source, and a graphite-based anode. They produced and then tested both pouch cell and coin cell battery prototypes.
After more than 100 charge-discharge cycles, Wang and colleagues observed no substantial capacity decay in the pouch cell. Additional experiments showed that the pouch cell still worked after being folded and cut in half. The coin cell retained 72% of its capacity after 300 charge-discharge cycles. They next applied the polymer coating to cathodes made from other metals, creating lithium-molybdenum and lithium-vanadium batteries. These cells also had stable capacity over 300 charge-discharge cycles. Overall, the results indicate that coated cathodes could produce not only safer Li-S batteries with long lifespans, but also efficient batteries with other metal sulfides, according to Wang’s team.
The authors acknowledge funding from the National Natural Science Foundation of China; the Natural Science Foundation of Sichuan, China; and the Beijing National Laboratory for Condensed Matter Physics.
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