Connect with us

TOP SCEINCE

Promethium bound: Rare earth element’s secrets exposed

Published

on

Promethium bound: Rare earth element’s secrets exposed


Scientists have uncovered the properties of a rare earth element that was first discovered 80 years ago at the very same laboratory, opening a new pathway for the exploration of elements critical in modern technology, from medicine to space travel.

Promethium was discovered in 1945 at Clinton Laboratories, now the Department of Energy’s Oak Ridge National Laboratory, and continues to be produced at ORNL in minute quantities. Some of its properties have remained elusive despite the rare earth element’s use in medical studies and long-lived nuclear batteries. It is named after the mythological Titan who delivered fire to humans and whose name symbolizes human striving.

“The whole idea was to explore this very rare element to gain new knowledge,” said Alex Ivanov, an ORNL scientist who co-led the research. “Once we realized it was discovered at this national lab and the place where we work, we felt an obligation to conduct this research to uphold the ORNL legacy.”

The ORNL-led team of scientists prepared a chemical complex of promethium, which enabled its characterization in solution for the first time. Thus, they exposed the secrets of this extremely rare lanthanide, whose atomic number is 61, in a series of meticulous experiments.

Their landmark study, published in the journal Nature, marks a significant advance in rare earth research and might rewrite chemistry textbooks.

“Because it has no stable isotopes, promethium was the last lanthanide to be discovered and has been the most difficult to study,” said ORNL’s Ilja Popovs, who co-led the research. Most rare earth elements are lanthanides, elements from 57 — lanthanum — to 71 — lutetium — on the periodic table. They have similar chemical properties but differ in size.

The other 14 lanthanides are well understood. They are metals with useful properties that make them indispensable in many modern technologies. They are workhorses of applications such as lasers, permanent magnets in wind turbines and electric vehicles, X-ray screens and even cancer-fighting medicines.

“There are thousands of publications on lanthanides’ chemistry without promethium. That was a glaring gap for all of science,” said ORNL’s Santa Jansone-Popova, who co-led the study. “Scientists have to assume most of its properties. Now we can actually measure some of them.”

The research relied on unique resources and expertise available at DOE national laboratories. Using a research reactor, hot cells and supercomputers, as well as the accumulated knowledge and skills of 18 scientists in different fields, the authors detailed the first observation of a promethium complex in solution.

The ORNL scientists bound, or chelated, radioactive promethium with special organic molecules called diglycolamide ligands. Then, using X-ray spectroscopy, they determined the properties of the complex, including the length of the promethium chemical bond with neighboring atoms — a first for science and a longstanding missing piece to the periodic table of elements.

Promethium is very rare; only about a pound occurs naturally in the Earth’s crust at any given time. Unlike other rare earth elements, only minute quantities of synthetic promethium are available because it has no stable isotopes.

For this study, the ORNL team produced the isotope promethium-147, with a half-life of 2.62 years, in sufficient quantities and at a high enough purity to study its chemical properties. ORNL is the United States’ only producer of promethium-147.

Notably, the team provided the first demonstration of a feature of lanthanide contraction in solution for the whole lanthanide series, including promethium, atomic number 61. Lanthanide contraction is a phenomenon in which elements with atomic numbers between 57 and 71 are smaller than expected. As the atomic numbers of these lanthanides increase, the radii of their ions decrease. This contraction creates distinctive chemical and electronic properties because the same charge is limited to a shrinking space. The ORNL scientists got a clear promethium signal, which enabled them to better define the shape of the trend — across the series.

“It’s really astonishing from a scientific viewpoint. I was struck once we had all the data,” said Ivanov. “The contraction of this chemical bond accelerates along this atomic series, but after promethium, it considerably slows down. This is an important landmark in understanding the chemical bonding properties of these elements and their structural changes along the periodic table.”

Many of these elements, such as those in the lanthanide and actinide series, have applications ranging from cancer diagnostics and treatment to renewable energy technologies and long-lived nuclear batteries for deep space exploration.

The achievement will, among other things, ease the difficult job of separating these valuable elements, according to Jansone-Popova. The team has long worked on separations for the whole series of lanthanides, “but promethium was the last puzzle piece. It was quite challenging,” she said. “You cannot utilize all these lanthanides as a mixture in modern advanced technologies, because first you need to separate them. This is where the contraction becomes very important; it basically allows us to separate them, which is still quite a difficult task.”

The research team used several premier DOE facilities in the project. At ORNL, promethium was synthesized at the High Flux Isotope Reactor, a DOE Office of Science user facility, and purified at the Radiochemical Engineering Development Center, a multipurpose radiochemical processing and research facility. Then, the team performed X-ray absorption spectroscopy at the National Synchrotron Light Source II, a DOE Office of Science user facility at DOE’s Brookhaven National Laboratory, specifically working at the Beamline for Materials Measurement, which is funded and operated by the National Institute of Standards and Technology.

The team also performed quantum chemical calculations and molecular dynamics simulations at the Oak Ridge Leadership Computing Facility, a DOE Office of Science user facility at ORNL, using the lab’s Summit supercomputer, the only computational resource capable of providing the necessary calculations at the time. In addition, the researchers used resources of the Compute and Data Environment for Science at ORNL. They expect future calculations to be performed on ORNL’s Frontier, the world’s most powerful supercomputer and the first exascale system, which is able to perform more than a quintillion calculations each second.

Popovs emphasized that the ORNL-led accomplishments can be attributed to teamwork. Each of the Nature paper’s 18 authors was critical to the project, he said.

The achievement sets the stage for a new era of research, the scientists said. “Anything that we would call a modern marvel of technology would include, in one shape or another, these rare earth elements,” Popovs said. “We are adding the missing link.”

Besides Popovs, Ivanov and Jansone-Popova from ORNL’s Chemical Sciences Division, the paper’s co-authors include Darren Driscoll, Subhamay Pramanik, Jeffrey Einkauf, Santanu Roy and Thomas Dyke, also of ORNL’s Chemical Sciences Division; Frankie White, Richard Mayes, Laetitia Delmau, Samantha Cary, April Miller and Sandra Davern of ORNL’s Radioisotope Science and Technology Division; Matt Silveira and Shelley VanCleve of ORNL’s Isotope Processing and Manufacturing Division; Dmytro Bykov of the National Center for Computational Sciences at ORNL; and Bruce Ravel of the National Institute of Standards and Technology.

This work was primarily co-sponsored by DOE’s Office of Science for ligand synthesis, lanthanide complexation studies, crystallization processes, spectroscopic analyses and simulation efforts. The production, purification and preparation of the promethium sample were supported by the DOE Isotope Program, managed by the Office of Science for Isotope R&D and Production. The single-crystal X-ray diffraction data collection and refinement were supported by the DOE Office of Science.



Source link

Continue Reading
Click to comment

Leave a Reply

TOP SCEINCE

Early dark energy could resolve cosmology’s two biggest puzzles

Published

on

By

Promethium bound: Rare earth element’s secrets exposed


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.

One puzzle in question is the “Hubble tension,” which refers to a mismatch in measurements of how fast the universe is expanding. The other involves observations of numerous early, bright galaxies that existed at a time when the early universe should have been much less populated.

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.



Source link

Continue Reading

TOP SCEINCE

Plant-derived secondary organic aerosols can act as mediators of plant-plant interactions

Published

on

By

Promethium bound: Rare earth element’s secrets exposed


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.

It is well known that plants release volatile organic compounds (VOCs) into the atmosphere when damaged by herbivores. These VOCs play a crucial role in plant-plant interactions, whereby undamaged plants may detect warning signals from their damaged neighbours and prepare their defences. “Reactive plant VOCs undergo oxidative chemical reactions, resulting in the formation of secondary organic aerosols (SOAs). We wondered whether the ecological functions mediated by VOCs persist after they are oxidated to form SOAs,” said Dr. Hao Yu, formerly a PhD student at UEF, but now at the University of Bern.

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.



Source link

Continue Reading

TOP SCEINCE

Folded or cut, this lithium-sulfur battery keeps going

Published

on

By

Promethium bound: Rare earth element’s secrets exposed


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.

Sulfur has been suggested as a material for lithium-ion batteries because of its low cost and potential to hold more energy than lithium-metal oxides and other materials used in traditional ion-based versions. To make Li-S batteries stable at high temperatures, researchers have previously proposed using a carbonate-based electrolyte to separate the two electrodes (an iron sulfide cathode and a lithium metal-containing anode). However, as the sulfide in the cathode dissolves into the electrolyte, it forms an impenetrable precipitate, causing the cell to quickly lose capacity. Liping Wang and colleagues wondered if they could add a layer between the cathode and electrolyte to reduce this corrosion without reducing functionality and rechargeability.

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.



Source link

Continue Reading

Trending