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    Using graphene foam to filter toxins from drinking water

    Some kinds of water pollution, such as algal blooms and plastics that foul rivers, lakes, and marine environments, lie in plain sight. But other contaminants are not so readily apparent, which makes their impact potentially more dangerous. Among these invisible substances is uranium. Leaching into water resources from mining operations, nuclear waste sites, or from natural subterranean deposits, the element can now be found flowing out of taps worldwide.

    In the United States alone, “many areas are affected by uranium contamination, including the High Plains and Central Valley aquifers, which supply drinking water to 6 million people,” says Ahmed Sami Helal, a postdoc in the Department of Nuclear Science and Engineering. This contamination poses a near and present danger. “Even small concentrations are bad for human health,” says Ju Li, the Battelle Energy Alliance Professor of Nuclear Science and Engineering and professor of materials science and engineering.

    Now, a team led by Li has devised a highly efficient method for removing uranium from drinking water. Applying an electric charge to graphene oxide foam, the researchers can capture uranium in solution, which precipitates out as a condensed solid crystal. The foam may be reused up to seven times without losing its electrochemical properties. “Within hours, our process can purify a large quantity of drinking water below the EPA limit for uranium,” says Li.

    A paper describing this work was published in this week Advanced Materials. The two first co-authors are Helal and Chao Wang, a postdoc at MIT during the study, who is now with the School of Materials Science and Engineering at Tongji University, Shanghai. Researchers from Argonne National Laboratory, Taiwan’s National Chiao Tung University, and the University of Tokyo also participated in the research. The Defense Threat Reduction Agency (U.S. Department of Defense) funded later stages of this work.

    Targeting the contaminant

    The project, launched three years ago, began as an effort to find better approaches to environmental cleanup of heavy metals from mining sites. To date, remediation methods for such metals as chromium, cadmium, arsenic, lead, mercury, radium, and uranium have proven limited and expensive. “These techniques are highly sensitive to organics in water, and are poor at separating out the heavy metal contaminants,” explains Helal. “So they involve long operation times, high capital costs, and at the end of extraction, generate more toxic sludge.”

    To the team, uranium seemed a particularly attractive target. Field testing from the U.S. Geological Service and the Environmental Protection Agency (EPA) has revealed unhealthy levels of uranium moving into reservoirs and aquifers from natural rock sources in the northeastern United States, from ponds and pits storing old nuclear weapons and fuel in places like Hanford, Washington, and from mining activities located in many western states. This kind of contamination is prevalent in many other nations as well. An alarming number of these sites show uranium concentrations close to or above the EPA’s recommended ceiling of 30 parts per billion (ppb) — a level linked to kidney damage, cancer risk, and neurobehavioral changes in humans.

    The critical challenge lay in finding a practical remediation process exclusively sensitive to uranium, capable of extracting it from solution without producing toxic residues. And while earlier research showed that electrically charged carbon fiber could filter uranium from water, the results were partial and imprecise.

    Wang managed to crack these problems — based on her investigation of the behavior of graphene foam used for lithium-sulfur batteries. “The physical performance of this foam was unique because of its ability to attract certain chemical species to its surface,” she says. “I thought the ligands in graphene foam would work well with uranium.”

    Simple, efficient, and clean

    The team set to work transforming graphene foam into the equivalent of a uranium magnet. They learned that by sending an electric charge through the foam, splitting water and releasing hydrogen, they could increase the local pH and induce a chemical change that pulled uranium ions out of solution. The researchers found that the uranium would graft itself onto the foam’s surface, where it formed a never-before-seen crystalline uranium hydroxide. On reversal of the electric charge, the mineral, which resembles fish scales, slipped easily off the foam.

    It took hundreds of tries to get the chemical composition and electrolysis just right. “We kept changing the functional chemical groups to get them to work correctly,” says Helal. “And the foam was initially quite fragile, tending to break into pieces, so we needed to make it stronger and more durable,” says Wang.

    This uranium filtration process is simple, efficient, and clean, according to Li: “Each time it’s used, our foam can capture four times its own weight of uranium, and we can achieve an extraction capacity of 4,000 mg per gram, which is a major improvement over other methods,” he says. “We’ve also made a major breakthrough in reusability, because the foam can go through seven cycles without losing its extraction efficiency.” The graphene foam functions as well in seawater, where it reduces uranium concentrations from 3 parts per million to 19.9 ppb, showing that other ions in the brine do not interfere with filtration.

    The team believes its low-cost, effective device could become a new kind of home water filter, fitting on faucets like those of commercial brands. “Some of these filters already have activated carbon, so maybe we could modify these, add low-voltage electricity to filter uranium,” says Li.

    “The uranium extraction this device achieves is very impressive when compared to existing methods,” says Ho Jin Ryu, associate professor of nuclear and quantum engineering at the Korea Advanced Institute of Science and Technology. Ryu, who was not involved in the research, believes that the demonstration of graphene foam reusability is a “significant advance,” and that “the technology of local pH control to enhance uranium deposition will be impactful because the scientific principle can be applied more generally to heavy metal extraction from polluted water.”

    The researchers have already begun investigating broader applications of their method. “There is a science to this, so we can modify our filters to be selective for other heavy metals such as lead, mercury, and cadmium,” says Li. He notes that radium is another significant danger for locales in the United States and elsewhere that lack resources for reliable drinking water infrastructure.

    “In the future, instead of a passive water filter, we could be using a smart filter powered by clean electricity that turns on electrolytic action, which could extract multiple toxic metals, tell you when to regenerate the filter, and give you quality assurance about the water you’re drinking.” More

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    A material difference

    Eesha Khare has always seen a world of matter. The daughter of a hardware engineer and a biologist, she has an insatiable interest in what substances — both synthetic and biological — have in common. Not surprisingly, that perspective led her to the study of materials.

    “I recognized early on that everything around me is a material,” she says. “How our phones respond to touches, how trees in nature to give us both structural wood and foldable paper, or how we are able to make high skyscrapers with steel and glass, it all comes down to the fundamentals: This is materials science and engineering.”

    As a rising fourth-year PhD student in the MIT Department of Materials Science and Engineering (DMSE), Khare now studies the metal-coordination bonds that allow mussels to bind to rocks along turbulent coastlines. But Khare’s scientific enthusiasm has also led to expansive interests from science policy to climate advocacy and entrepreneurship.

    A material world

    A Silicon Valley native, Khare recalls vividly how excited she was about science as a young girl, both at school and at myriad science fairs and high school laboratory internships. One such internship at the University of California at Santa Cruz introduced her to the study of nanomaterials, or materials that are smaller than a single human cell. The project piqued her interest in how research could lead to energy-storage applications, and she began to ponder the connections between materials, science policy, and the environment.

    As an undergraduate at Harvard University, Khare pursued a degree in engineering sciences and chemistry while also working at the Harvard Kennedy School Institute of Politics. There, she grew fascinated by environmental advocacy in the policy space, working for then-professor Gina McCarthy, who is currently serving in the Biden administration as the first-ever White House climate advisor.

    Following her academic explorations in college, Khare wanted to consider science in a new light before pursuing her doctorate in materials science and engineering. She deferred her program acceptance at MIT in order to attend Cambridge University in the U.K., where she earned a master’s degree in the history and philosophy of science. “Especially in a PhD program, it can often feel like your head is deep in the science as you push new research frontiers, but I wanted take a step back and be inspired by how scientists in the past made their discoveries,” she says.

    Her experience at Cambridge was both challenging and informative, but Khare quickly found that her mechanistic curiosity remained persistent — a realization that came in the form of a biological material.

    “My very first master’s research project was about environmental pollution indicators in the U.K., and I was looking specifically at lichen to understand the social and political reasons why they were adopted by the public as pollution indicators,” Khare explains. “But I found myself wondering more about how lichen can act as pollution indicators. And I found that to be quite similar for most of my research projects: I was more interested in how the technology or discovery actually worked.”

    Enthusiasm for innovation

    Fittingly, these bioindicators confirmed for her that studying materials at MIT was the right course. Now Khare works on a different organism altogether, conducting research on the metal-coordination chemical interactions of a biopolymer secreted by mussels.

    “Mussels secrete this thread and can adhere to ocean walls. So, when ocean waves come, mussels don’t get dislodged that easily,” Khare says. “This is partly because of how metal ions in this material bind to different amino acids in the protein. There’s no input from the mussel itself to control anything there; all the magic is in this biological material that is not only very sticky, but also doesn’t break very readily, and if you cut it, it can re-heal that interface as well! If we could better understand and replicate this biological material in our own world, we could have materials self-heal and never break and thus eliminate so much waste.”

    To study this natural material, Khare combines computational and experimental techniques, experimentally synthesizing her own biopolymers and studying their properties with in silico molecular dynamics. Her co-advisors — Markus Buehler, the Jerry McAfee Professor of Engineering in Civil and Environmental Engineering, and Niels Holten-Andersen, professor of materials science and engineering — have embraced this dual-approach to her project, as well as her abundant enthusiasm for innovation.

    Khare likes to take one exploratory course per semester, and a recent offering in the MIT Sloan School of Management inspired her to pursue entrepreneurship. These days she is spending much of her free time on a startup called Taxie, formed with fellow MIT students after taking the course 15.390 (New Enterprises). Taxie attempts to electrify the rideshare business by making electric rental cars available to rideshare drivers. Khare hopes this project will initiate some small first steps in making the ridesharing industry environmentally cleaner — and in democratizing access to electric vehicles for rideshare drivers, who often hail from lower-income or immigrant backgrounds.

    “There are a lot of goals thrown around for reducing emissions or helping our environment. But we are slowly getting physical things on the road, physical things to real people, and I like to think that we are helping to accelerate the electric transition,” Khare says. “These small steps are helpful for learning, at the very least, how we can make a transition to electric or to a cleaner industry.”

    Alongside her startup work, Khare has pursued a number of other extracurricular activities at MIT, including co-organizing her department’s Student Application Assistance Program and serving on DMSE’s Diversity, Equity, and Inclusion Council. Her varied interests also have led to a diverse group of friends, which suits her well, because she is a self-described “people-person.”

    In a year where maintaining connections has been more challenging than usual, Khare has focused on the positive, spending her spring semester with family in California and practicing Bharatanatyam, a form of Indian classical dance, over Zoom. As she looks to the future, Khare hopes to bring even more of her interests together, like materials science and climate.

    “I want to understand the energy and environmental sector at large to identify the most pressing technology gaps and how can I use my knowledge to contribute. My goal is to figure out where can I personally make a difference and where it can have a bigger impact to help our climate,” she says. “I like being outside of my comfort zone.” More

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    Reducing emissions by decarbonizing industry

    A critical challenge in meeting the Paris Agreement’s long-term goal of keeping global warming well below 2 degrees Celsius is to vastly reduce carbon dioxide (CO2) and other greenhouse gas emissions generated by the most energy-intensive industries. According to a recent report by the International Energy Agency, these industries — cement, iron and steel, chemicals — account for about 20 percent of global CO2 emissions. Emissions from these industries are notoriously difficult to abate because, in addition to emissions associated with energy use, a significant portion of industrial emissions come from the process itself.

    For example, in the cement industry, about half the emissions come from the decomposition of limestone into lime and CO2. While a shift to zero-carbon energy sources such as solar or wind-powered electricity could lower CO2 emissions in the power sector, there are no easy substitutes for emissions-intensive industrial processes.

    Enter industrial carbon capture and storage (CCS). This technology, which extracts point-source carbon emissions and sequesters them underground, has the potential to remove up to 90-99 percent of CO2 emissions from an industrial facility, including both energy-related and process emissions. And that begs the question: Might CCS alone enable hard-to-abate industries to continue to grow while eliminating nearly all of the CO2 emissions they generate from the atmosphere?

    The answer is an unequivocal yes in a new study in the journal Applied Energy co-authored by researchers at the MIT Joint Program on the Science and Policy of Global Change, MIT Energy Initiative, and ExxonMobil.

    Using an enhanced version of the MIT Economic Projection and Policy Analysis (EPPA) model that represents different industrial CCS technology choices — and assuming that CCS is the only greenhouse gas emissions mitigation option available to hard-to-abate industries — the study assesses the long-term economic and environmental impacts of CCS deployment under a climate policy aimed at capping the rise in average global surface temperature at 2 C above preindustrial levels.

    The researchers find that absent industrial CCS deployment, the global costs of implementing the 2 C policy are higher by 12 percent in 2075 and 71 percent in 2100, relative to policy costs with CCS. They conclude that industrial CCS enables continued growth in the production and consumption of energy-intensive goods from hard-to-abate industries, along with dramatic reductions in the CO2 emissions they generate. Their projections show that as industrial CCS gains traction mid-century, this growth occurs globally as well as within geographical regions (primarily in China, Europe, and the United States) and the cement, iron and steel, and chemical sectors.

    “Because it can enable deep reductions in industrial emissions, industrial CCS is an essential mitigation option in the successful implementation of policies aligned with the Paris Agreement’s long-term climate targets,” says Sergey Paltsev, the study’s lead author and a deputy director of the MIT Joint Program and senior research scientist at the MIT Energy Initiative. “As the technology advances, our modeling approach offers decision-makers a pathway for projecting the deployment of industrial CCS across industries and regions.”

    But such advances will not take place without substantial, ongoing funding.

    “Sustained government policy support across decades will be needed if CCS is to realize its potential to promote the growth of energy-intensive industries and a stable climate,” says Howard Herzog, a co-author of the study and senior research engineer at the MIT Energy Initiative.

    The researchers also find that advanced CCS options such as cryogenic carbon capture (CCC), in which extracted CO2 is cooled to solid form using far less power than conventional coal- and gas-fired CCS technologies, could help expand the use of CCS in industrial settings through further production cost and emissions reductions.

    The study was supported by sponsors of the MIT Joint Program and by ExxonMobil through its membership in the MIT Energy Initiative. More