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      in Environment

      Nanotube sensors are capable of detecting and distinguishing gibberellin plant hormones

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      Researchers from the Disruptive and Sustainable Technologies for Agricultural Precision (DiSTAP) interdisciplinary research group of the Singapore-MIT Alliance for Research and Technology (SMART), MIT’s research enterprise in Singapore, and their collaborators from Temasek Life Sciences Laboratory have developed the first-ever nanosensor that can detect and distinguish gibberellins (GAs), a class of hormones in plants that are important for growth. The novel nanosensors are nondestructive, unlike conventional collection methods, and have been successfully tested in living plants. Applied in the field for early-stage plant stress monitoring, the sensors could prove transformative for agriculture and plant biotechnology, giving farmers interested in high-tech precision agriculture and crop management a valuable tool to optimize yield.

      The researchers designed near-infrared fluorescent carbon nanotube sensors that are capable of detecting and distinguishing two plant hormones, GA3 and GA4. Belonging to a class of plant hormones known as gibberellins, GA3 and GA4 are diterpenoid phytohormones produced by plants that play an important role in modulating diverse processes involved in plant growth and development. GAs are thought to have played a role in the driving forces behind the “green revolution” of the 1960s, which was in turn credited with averting famine and saving the lives of many worldwide. The continued study of gibberellins could lead to further breakthroughs in agricultural science and have implications for food security.

      Climate change, global warming, and rising sea levels cause farming soil to get contaminated by saltwater, raising soil salinity. In turn, high soil salinity is known to negatively regulate GA biosynthesis and promote GA metabolism, resulting in the reduction of GA content in plants. The new nanosensors developed by the SMART researchers allow for the study of GA dynamics in living plants under salinity stress at a very early stage, potentially enabling farmers to make early interventions when eventually applied in the field. This forms the basis of early-stage stress detection.

      Currently, methods to detect GA3 and GA4 typically require mass spectroscopy-based analysis, a time-consuming and destructive process. In contrast, the new sensors developed by the researchers are highly selective for the respective GAs and offer real-time, in vivo monitoring of changes in GA levels across a broad range of plant species.

      Described in a paper titled “Near-Infrared Fluorescent Carbon Nanotube Sensors for the Plant Hormone Family Gibberellins” published in the journal Nano Letters, the research represents a breakthrough for early-stage plant stress detection and holds tremendous potential to advance plant biotechnology and agriculture. This paper builds on previous research by the team at SMART DiSTAP on single-walled carbon nanotube-based nanosensors using the corona phase molecular recognition (CoPhMoRe) platform.

      Based on the CoPhMoRe concept introduced by the lab of MIT Professor Professor Michael Strano, the novel sensors are able to detect GA kinetics in the roots of a variety of model and non-model plant species, including Arabidopsis, lettuce, and basil, as well as GA accumulation during lateral root emergence, highlighting the importance of GA in root system architecture. This was made possible by the researchers’ related development of a new coupled Raman/near infrared fluorimeter that enables self-referencing of nanosensor near infrared fluorescence with its Raman G-band, a new hardware innovation that removes the need for a separate reference nanosensor and greatly simplifies the instrumentation requirements by using a single optical channel to measure hormone concentration.

      Using the reversible GA nanosensors, the researchers detected increased endogenous GA levels in mutant plants producing greater amounts of GA20ox1, a key enzyme in GA biosynthesis, as well as decreased GA levels in plants under salinity stress. When exposed to salinity stress, researchers also found that lettuce growth was severely stunted — an indication that only became apparent after 10 days. In contrast, the GA nanosensors reported decreased GA levels after just six hours, demonstrating their efficacy as a much earlier indicator of salinity stress.

      “Our CoPhMoRe technique allows us to create nanoparticles that act like natural antibodies in that they can recognize and lock onto specific molecules. But they tend to be far more stable than alternatives. We have used this method to successfully create nanosensors for plant signals such as hydrogen peroxide and heavy-metal pollutants like arsenic in plants and soil,” says Strano, the Carbon P. Dubbs Professor of Chemical Engineering at MIT who is co-corresponding author and DiSTAP co-lead principal investigator. “The method works to create sensors for organic molecules like synthetic auxin — an important plant hormone — as we have shown. This latest breakthrough now extends this success to a plant hormone family called gibberellins — an exceedingly difficult one to recognize.”

      Strano adds: “The resulting technology offers a rapid, real-time, and in vivo method to monitor changes in GA levels in virtually any plant, and can replace current sensing methods which are laborious, destructive, species-specific, and much less efficient.”

      Mervin Chun-Yi Ang, associate scientific director at DiSTAP and co-first author of the paper, says, “More than simply a breakthrough in plant stress detection, we have also demonstrated a hardware innovation in the form of a new coupled Raman/NIR fluorimeter that enabled self-referencing of SWNT sensor fluorescence with its Raman G-band, representing a major advance in the translation of our nanosensing tool sets to the field. In the near future, our sensors can be combined with low-cost electronics, portable optodes, or microneedle interfaces for industrial use, transforming how the industry screens for and mitigates plant stress in food crops and potentially improving growth and yield.”

      The new sensors could yet have a variety of industrial applications and use cases. Daisuke Urano, a Temasek Life Sciences Laboratory principal investigator, National University of Singapore (NUS) adjunct assistant professor, and co-corresponding author of the paper, explains, “GAs are known to regulate a wide range of plant development processes, from shoot, root, and flower development, to seed germination and plant stress responses. With the commercialization of GAs, these plant hormones are also sold to growers and farmers as plant growth regulators to promote plant growth and seed germination. Our novel GA nanosensors could be applied in the field for early-stage plant stress monitoring, and also be used by growers and farmers to track the uptake or metabolism of GA in their crops.”

      The design and development of the nanosensors, creation and validation of the coupled Raman/near infrared fluorimeter and related image/data processing algorithms, as well as statistical analysis of readouts from plant sensors for this study were performed by SMART and MIT. The Temasek Life Sciences Laboratory was responsible for the design, execution, and analysis of plant-related studies, including validation of nanosensors in living plants.

      This research was carried out by SMART and supported by the National Research Foundation of Singapore under its Campus for Research Excellence And Technological Enterprise (CREATE) program. The DiSTAP program, led by Strano and Singapore co-lead principal investigator Professor Chua Nam Hai, addresses deep problems in food production in Singapore and the world by developing a suite of impactful and novel analytical, genetic, and biomaterial technologies. The goal is to fundamentally change how plant biosynthetic pathways are discovered, monitored, engineered, and ultimately translated to meet the global demand for food and nutrients. Scientists from MIT, Temasek Life Sciences Laboratory, Nanyang Technological University (NTU) and NUS are collaboratively developing new tools for the continuous measurement of important plant metabolites and hormones for novel discovery, deeper understanding and control of plant biosynthetic pathways in ways not yet possible, especially in the context of green leafy vegetables; leveraging these new techniques to engineer plants with highly desirable properties for global food security, including high yield density production, and drought and pathogen resistance, and applying these technologies to improve urban farming.

      SMART was established by MIT and the National Research Foundation of Singapore in 2007. SMART serves as an intellectual and innovation hub for research interactions between MIT and Singapore, undertaking cutting-edge research projects in areas of interest to both Singapore and MIT. SMART currently comprises an Innovation Center and five interdisciplinary research groups: Antimicrobial Resistance, Critical Analytics for Manufacturing Personalized-Medicine, DiSTAP, Future Urban Mobility, and Low Energy Electronic Systems. More

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      in Environment

      Aviva Intveld named 2023 Gates Cambridge Scholar

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      MIT senior Aviva Intveld has won the prestigious Gates Cambridge Scholarship, which offers students an opportunity to pursue graduate study in the field of their choice at Cambridge University in the U.K. Intveld will join the other 23 U.S. citizens selected for the 2023 class of scholars.

      Intveld, from Los Angeles, is majoring in earth, atmospheric, and planetary sciences, and minoring in materials science and engineering with concentrations in geology, geochemistry, and archaeology. Her research interests span the intersections among those fields to better understand how the natural environments of the past have shaped human movement and decision-making.

      At Cambridge, Intveld will undertake a research MPhil in earth sciences at the Godwin Lab for Paleoclimate Research, where she will investigate the impact of past climate on the ancient Maya in northwest Yucatán via cave sediment records. She hopes to pursue an impact-oriented research career in paleoclimate and paleoenvironment reconstruction and ultimately apply the lessons learned from her research to inform modern climate policy. She is particularly passionate about sustainable mining of energy-critical elements and addressing climate change inequality in her home state of California.

      Intveld’s work at Cambridge will build upon her extensive research experience at MIT. She currently works in the McGee Lab reconstructing the Late Pleistocene-Early Holocene paleoclimate of northeastern Mexico to provide a climatic background to the first peopling of the Americas. Previously, she explored the influence of mountain plate tectonics on biodiversity in the Perron Lab. During a summer research position at the University of Haifa in Israel she analyzed the microfossil assemblage of an offshore sediment core for paleo-coastal reconstruction.

      Last summer, Intveld interned at the National Oceanic and Atmospheric Administration in Homer, Alaska, to identify geologic controls on regional groundwater chemistry. She has also interned with the World Wildlife Fund and with the Natural History Museum of Los Angeles. During her the spring semester of her junior year, Intveld studied abroad through MISTI at Imperial College London’s Royal School of Mines and completed geology field work in Sardinia, Italy.

      Intveld has been a strong presence on MIT’s campus, serving as the undergraduate representative on the EAPS Diversity, Equity, and Inclusion Committee. She leads tours for the MIT List Visual Arts Center, is a member of and associate advisor for the Terrascope Learning Community, and is a participant in the Addir Interfaith Dialogue Fellowship.

      Inveld was advised in her application by Kim Benard, associate dean of the Distinguished Fellowships team in Career Advising and Professional Development, who says, “Aviva’s work is at a fascinating crossroads of archeology, geology, and sustainability. She has already done extraordinary work, and this opportunity will prepare her even more to be influential in the fight for climate mitigation.”

      Established by the Bill and Melinda Gates Foundation in 2000, the Gates Cambridge Scholarship provides full funding for talented students from outside the United Kingdom to pursue postgraduate study in any subject at Cambridge University. Since the program’s inception in 2001, there have been 33 Gates Cambridge Scholars from MIT. More

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      in Energy

      Integrating humans with AI in structural design

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      Modern fabrication tools such as 3D printers can make structural materials in shapes that would have been difficult or impossible using conventional tools. Meanwhile, new generative design systems can take great advantage of this flexibility to create innovative designs for parts of a new building, car, or virtually any other device.

      But such “black box” automated systems often fall short of producing designs that are fully optimized for their purpose, such as providing the greatest strength in proportion to weight or minimizing the amount of material needed to support a given load. Fully manual design, on the other hand, is time-consuming and labor-intensive.

      Now, researchers at MIT have found a way to achieve some of the best of both of these approaches. They used an automated design system but stopped the process periodically to allow human engineers to evaluate the work in progress and make tweaks or adjustments before letting the computer resume its design process. Introducing a few of these iterations produced results that performed better than those designed by the automated system alone, and the process was completed more quickly compared to the fully manual approach.

      The results are reported this week in the journal Structural and Multidisciplinary Optimization, in a paper by MIT doctoral student Dat Ha and assistant professor of civil and environmental engineering Josephine Carstensen.

      The basic approach can be applied to a broad range of scales and applications, Carstensen explains, for the design of everything from biomedical devices to nanoscale materials to structural support members of a skyscraper. Already, automated design systems have found many applications. “If we can make things in a better way, if we can make whatever we want, why not make it better?” she asks.

      “It’s a way to take advantage of how we can make things in much more complex ways than we could in the past,” says Ha, adding that automated design systems have already begun to be widely used over the last decade in automotive and aerospace industries, where reducing weight while maintaining structural strength is a key need.

      “You can take a lot of weight out of components, and in these two industries, everything is driven by weight,” he says. In some cases, such as internal components that aren’t visible, appearance is irrelevant, but for other structures aesthetics may be important as well. The new system makes it possible to optimize designs for visual as well as mechanical properties, and in such decisions the human touch is essential.

      As a demonstration of their process in action, the researchers designed a number of structural load-bearing beams, such as might be used in a building or a bridge. In their iterations, they saw that the design has an area that could fail prematurely, so they selected that feature and required the program to address it. The computer system then revised the design accordingly, removing the highlighted strut and strengthening some other struts to compensate, and leading to an improved final design.

      The process, which they call Human-Informed Topology Optimization, begins by setting out the needed specifications — for example, a beam needs to be this length, supported on two points at its ends, and must support this much of a load. “As we’re seeing the structure evolve on the computer screen in response to initial specification,” Carstensen says, “we interrupt the design and ask the user to judge it. The user can select, say, ‘I’m not a fan of this region, I’d like you to beef up or beef down this feature size requirement.’ And then the algorithm takes into account the user input.”

      While the result is not as ideal as what might be produced by a fully rigorous yet significantly slower design algorithm that considers the underlying physics, she says it can be much better than a result generated by a rapid automated design system alone. “You don’t get something that’s quite as good, but that was not necessarily the goal. What we can show is that instead of using several hours to get something, we can use 10 minutes and get something much better than where we started off.”

      The system can be used to optimize a design based on any desired properties, not just strength and weight. For example, it can be used to minimize fracture or buckling, or to reduce stresses in the material by softening corners.

      Carstensen says, “We’re not looking to replace the seven-hour solution. If you have all the time and all the resources in the world, obviously you can run these and it’s going to give you the best solution.” But for many situations, such as designing replacement parts for equipment in a war zone or a disaster-relief area with limited computational power available, “then this kind of solution that catered directly to your needs would prevail.”

      Similarly, for smaller companies manufacturing equipment in essentially “mom and pop” businesses, such a simplified system might be just the ticket. The new system they developed is not only simple and efficient to run on smaller computers, but it also requires far less training to produce useful results, Carstensen says. A basic two-dimensional version of the software, suitable for designing basic beams and structural parts, is freely available now online, she says, as the team continues to develop a full 3D version.

      “The potential applications of Prof Carstensen’s research and tools are quite extraordinary,” says Christian Málaga-Chuquitaype, a professor of civil and environmental engineering at Imperial College London, who was not associated with this work. “With this work, her group is paving the way toward a truly synergistic human-machine design interaction.”

      “By integrating engineering ‘intuition’ (or engineering ‘judgement’) into a rigorous yet computationally efficient topology optimization process, the human engineer is offered the possibility of guiding the creation of optimal structural configurations in a way that was not available to us before,” he adds. “Her findings have the potential to change the way engineers tackle ‘day-to-day’ design tasks.” More

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      in Environment

      Improving health outcomes by targeting climate and air pollution simultaneously

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      Climate policies are typically designed to reduce greenhouse gas emissions that result from human activities and drive climate change. The largest source of these emissions is the combustion of fossil fuels, which increases atmospheric concentrations of ozone, fine particulate matter (PM2.5) and other air pollutants that pose public health risks. While climate policies may result in lower concentrations of health-damaging air pollutants as a “co-benefit” of reducing greenhouse gas emissions-intensive activities, they are most effective at improving health outcomes when deployed in tandem with geographically targeted air-quality regulations.

      Yet the computer models typically used to assess the likely air quality/health impacts of proposed climate/air-quality policy combinations come with drawbacks for decision-makers. Atmospheric chemistry/climate models can produce high-resolution results, but they are expensive and time-consuming to run. Integrated assessment models can produce results for far less time and money, but produce results at global and regional scales, rendering them insufficiently precise to obtain accurate assessments of air quality/health impacts at the subnational level.

      To overcome these drawbacks, a team of researchers at MIT and the University of California at Davis has developed a climate/air-quality policy assessment tool that is both computationally efficient and location-specific. Described in a new study in the journal ACS Environmental Au, the tool could enable users to obtain rapid estimates of combined policy impacts on air quality/health at more than 1,500 locations around the globe — estimates precise enough to reveal the equity implications of proposed policy combinations within a particular region.

      “The modeling approach described in this study may ultimately allow decision-makers to assess the efficacy of multiple combinations of climate and air-quality policies in reducing the health impacts of air pollution, and to design more effective policies,” says Sebastian Eastham, the study’s lead author and a principal research scientist at the MIT Joint Program on the Science and Policy of Global Change. “It may also be used to determine if a given policy combination would result in equitable health outcomes across a geographical area of interest.”

      To demonstrate the efficiency and accuracy of their policy assessment tool, the researchers showed that outcomes projected by the tool within seconds were consistent with region-specific results from detailed chemistry/climate models that took days or even months to run. While continuing to refine and develop their approaches, they are now working to embed the new tool into integrated assessment models for direct use by policymakers.

      “As decision-makers implement climate policies in the context of other sustainability challenges like air pollution, efficient modeling tools are important for assessment — and new computational techniques allow us to build faster and more accurate tools to provide credible, relevant information to a broader range of users,” says Noelle Selin, a professor at MIT’s Institute for Data, Systems and Society and Department of Earth, Atmospheric and Planetary Sciences, and supervising author of the study. “We are looking forward to further developing such approaches, and to working with stakeholders to ensure that they provide timely, targeted and useful assessments.”

      The study was funded, in part, by the U.S. Environmental Protection Agency and the Biogen Foundation. More

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      in Environment

      Study: Carbon-neutral pavements are possible by 2050, but rapid policy and industry action are needed

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      Almost 2.8 million lane-miles, or about 4.6 million lane-kilometers, of the United States are paved.

      Roads and streets form the backbone of our built environment. They take us to work or school, take goods to their destinations, and much more.

      However, a new study by MIT Concrete Sustainability Hub (CSHub) researchers shows that the annual greenhouse gas (GHG) emissions of all construction materials used in the U.S. pavement network are 11.9 to 13.3 megatons. This is equivalent to the emissions of a gasoline-powered passenger vehicle driving about 30 billion miles in a year.

      As roads are built, repaved, and expanded, new approaches and thoughtful material choices are necessary to dampen their carbon footprint. 

      The CSHub researchers found that, by 2050, mixtures for pavements can be made carbon-neutral if industry and governmental actors help to apply a range of solutions — like carbon capture — to reduce, avoid, and neutralize embodied impacts. (A neutralization solution is any compensation mechanism in the value chain of a product that permanently removes the global warming impact of the processes after avoiding and reducing the emissions.) Furthermore, nearly half of pavement-related greenhouse gas (GHG) savings can be achieved in the short term with a negative or nearly net-zero cost.

      The research team, led by Hessam AzariJafari, MIT CSHub’s deputy director, closed gaps in our understanding of the impacts of pavements decisions by developing a dynamic model quantifying the embodied impact of future pavements materials demand for the U.S. road network. 

      The team first split the U.S. road network into 10-mile (about 16 kilometer) segments, forecasting the condition and performance of each. They then developed a pavement management system model to create benchmarks helping to understand the current level of emissions and the efficacy of different decarbonization strategies. 

      This model considered factors such as annual traffic volume and surface conditions, budget constraints, regional variation in pavement treatment choices, and pavement deterioration. The researchers also used a life-cycle assessment to calculate annual state-level emissions from acquiring pavement construction materials, considering future energy supply and materials procurement.

      The team considered three scenarios for the U.S. pavement network: A business-as-usual scenario in which technology remains static, a projected improvement scenario aligned with stated industry and national goals, and an ambitious improvement scenario that intensifies or accelerates projected strategies to achieve carbon neutrality. 

      If no steps are taken to decarbonize pavement mixtures, the team projected that GHG emissions of construction materials used in the U.S. pavement network would increase by 19.5 percent by 2050. Under the projected scenario, there was an estimated 38 percent embodied impact reduction for concrete and 14 percent embodied impact reduction for asphalt by 2050.

      The keys to making the pavement network carbon neutral by 2050 lie in multiple places. Fully renewable energy sources should be used for pavement materials production, transportation, and other processes. The federal government must contribute to the development of these low-carbon energy sources and carbon capture technologies, as it would be nearly impossible to achieve carbon neutrality for pavements without them. 

      Additionally, increasing pavements’ recycled content and improving their design and production efficiency can lower GHG emissions to an extent. Still, neutralization is needed to achieve carbon neutrality.

      Making the right pavement construction and repair choices would also contribute to the carbon neutrality of the network. For instance, concrete pavements can offer GHG savings across the whole life cycle as they are stiffer and stay smoother for longer, meaning they require less maintenance and have a lesser impact on the fuel efficiency of vehicles. 

      Concrete pavements have other use-phase benefits including a cooling effect through an intrinsically high albedo, meaning they reflect more sunlight than regular pavements. Therefore, they can help combat extreme heat and positively affect the earth’s energy balance through positive radiative forcing, making albedo a potential neutralization mechanism.

      At the same time, a mix of fixes, including using concrete and asphalt in different contexts and proportions, could produce significant GHG savings for the pavement network; decision-makers must consider scenarios on a case-by-case basis to identify optimal solutions. 

      In addition, it may appear as though the GHG emissions of materials used in local roads are dwarfed by the emissions of interstate highway materials. However, the study found that the two road types have a similar impact. In fact, all road types contribute heavily to the total GHG emissions of pavement materials in general. Therefore, stakeholders at the federal, state, and local levels must be involved if our roads are to become carbon neutral. 

      The path to pavement network carbon-neutrality is, therefore, somewhat of a winding road. It demands regionally specific policies and widespread investment to help implement decarbonization solutions, just as renewable energy initiatives have been supported. Providing subsidies and covering the costs of premiums, too, are vital to avoid shifts in the market that would derail environmental savings.

      When planning for these shifts, we must recall that pavements have impacts not just in their production, but across their entire life cycle. As pavements are used, maintained, and eventually decommissioned, they have significant impacts on the surrounding environment.

      If we are to meet climate goals such as the Paris Agreement, which demands that we reach carbon-neutrality by 2050 to avoid the worst impacts of climate change, we — as well as industry and governmental stakeholders — must come together to take a hard look at the roads we use every day and work to reduce their life cycle emissions. 

      The study was published in the International Journal of Life Cycle Assessment. In addition to AzariJafari, the authors include Fengdi Guo of the MIT Department of Civil and Environmental Engineering; Jeremy Gregory, executive director of the MIT Climate and Sustainability Consortium; and Randolph Kirchain, director of the MIT CSHub. More

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      in Energy

      A more sustainable way to generate phosphorus

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      Phosphorus is an essential ingredient in thousands of products, including herbicides, lithium-ion batteries, and even soft drinks. Most of this phosphorus comes from an energy-intensive process that contributes significantly to global carbon emissions.

      In an effort to reduce that carbon footprint, MIT chemists have devised an alternative way to generate white phosphorus, a critical intermediate in the manufacture of those phosphorus-containing products. Their approach, which uses electricity to speed up a key chemical reaction, could reduce the carbon emissions of the process by half or even more, the researchers say.

      “White phosphorus is currently an indispensable intermediate, and our process dramatically reduces the carbon footprint of converting phosphate to white phosphorus,” says Yogesh Surendranath, an associate professor of chemistry at MIT and the senior author of the study.

      The new process reduces the carbon footprint of white phosphorus production in two ways: It reduces the temperatures required for the reaction, and it generates significantly less carbon dioxide as a waste product.

      Recent MIT graduate Jonathan “Jo” Melville PhD ’21 and MIT graduate student Andrew Licini are the lead authors of the paper, which appears today in ACS Central Science.

      Purifying phosphorus

      When phosphorus is mined out of the ground, it is in the form of phosphate, a mineral whose basic unit comprises one atom of phosphorus bound to four oxygen atoms. About 95 percent of this phosphate ore is used to make fertilizer. The remaining phosphate ore is processed separately into white phosphorus, a molecule composed of four phosphorus atoms bound to each other. White phosphorus is then fed into a variety of chemical processes that are used to manufacture many different products, such as lithium battery electrolytes and semiconductor dopants.

      Converting those mined phosphates into white phosphorus accounts for a substantial fraction of the carbon footprint of the entire phosphorus industry, Surendranath says. The most energy-intensive part of the process is breaking the bonds between phosphorus and oxygen, which are very stable.

      Using the traditional “thermal process,” those bonds are broken by heating carbon coke and phosphate rock to a temperature of 1,500 degrees Celsius. In this process, the carbon serves to strip away the oxygen atoms from phosphorus, leading to the eventual generation of CO2 as a byproduct. In addition, sustaining those temperatures requires a great deal of energy, adding to the carbon footprint of the process.

      “That process hasn’t changed substantially since its inception over a century ago. Our goal was to figure out how we could develop a process that would substantially lower the carbon footprint of this process,” Surendranath says. “The idea was to combine it with renewable electricity and drive that conversion of phosphate to white phosphorus with electrons rather than using carbon.”

      To do that, the researchers had to come up with an alternative way to weaken the strong phosphorus-oxygen bonds found in phosphates. They achieved this by controlling the environment in which the reaction occurs. The researchers found that the reaction could be promoted using a dehydrated form of phosphoric acid, which contains long chains of phosphate salts held together by bonds called phosphoryl anhydrides. These bonds help to weaken the phosphorus-oxygen bonds.

      When the researchers run an electric current through these salts, electrons break the weakened bonds, allowing the phosphorus atoms to break free and bind to each other to form white phosphorus. At the temperatures needed for this system (about 800 C), phosphorus exists as a gas, so it can bubble out of the solution and be collected in an external chamber.

      Decarbonization

      The electrode that the researchers used for this demonstration relies on carbon as a source of electrons, so the process generates some carbon dioxide as a byproduct. However, they are now working on swapping that electrode out for one that would use phosphate itself as the electron source, which would further reduce the carbon footprint by cleanly separating phosphate into phosphorus and oxygen.

      With the process reported in this paper, the researchers have reduced the overall carbon footprint for generating white phosphorus by about 50 percent. With future modifications, they hope to bring the carbon emissions down to nearly zero, in part by using renewable energy such as solar or wind power to drive the electric current required.

      If the researchers succeed in scaling up their process and making it widely available, it could allow industrial users to generate white phosphorus on site instead of having it shipped from the few places in the world where it is currently manufactured. That would cut down on the risks of transporting white phosphorus, which is an explosive material.

      “We’re excited about the prospect of doing on-site generation of this intermediate, so you don’t have to do the transportation and distribution,” Surendranath says. “If you could decentralize this production, the end user could make it on site and use it in an integrated fashion.”

      In order to do this study, the researchers had to develop new tools for controlling the electrolytes (such as salts and acids) present in the environment, and for measuring how those electrolytes affect the reaction. Now, they plan to use the same approach to try to develop lower-carbon processes for isolating other industrially important elements, such as silicon and iron.

      “This work falls within our broader interests in decarbonizing these legacy industrial processes that have a huge carbon footprint,” Surendranath says. “The basic science that leads us there is understanding how you can tailor the electrolytes to foster these processes.”

      The research was funded by the UMRP Partnership for Progress on Sustainable Development in Africa, a fellowship from the MIT Tata Center for Technology and Design, and a National Defense Science and Engineering Graduate Fellowship. More

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      in Energy

      Using combustion to make better batteries

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      For more than a century, much of the world has run on the combustion of fossil fuels. Now, to avert the threat of climate change, the energy system is changing. Notably, solar and wind systems are replacing fossil fuel combustion for generating electricity and heat, and batteries are replacing the internal combustion engine for powering vehicles. As the energy transition progresses, researchers worldwide are tackling the many challenges that arise.

      Sili Deng has spent her career thinking about combustion. Now an assistant professor in the MIT Department of Mechanical Engineering and the Class of 1954 Career Development Professor, Deng leads a group that, among other things, develops theoretical models to help understand and control combustion systems to make them more efficient and to control the formation of emissions, including particles of soot.

      “So we thought, given our background in combustion, what’s the best way we can contribute to the energy transition?” says Deng. In considering the possibilities, she notes that combustion refers only to the process — not to what’s burning. “While we generally think of fossil fuels when we think of combustion, the term ‘combustion’ encompasses many high-temperature chemical reactions that involve oxygen and typically emit light and large amounts of heat,” she says.

      Given that definition, she saw another role for the expertise she and her team have developed: They could explore the use of combustion to make materials for the energy transition. Under carefully controlled conditions, combusting flames can be used to produce not polluting soot, but rather valuable materials, including some that are critical in the manufacture of lithium-ion batteries.

      Improving the lithium-ion battery by lowering costs

      The demand for lithium-ion batteries is projected to skyrocket in the coming decades. Batteries will be needed to power the growing fleet of electric cars and to store the electricity produced by solar and wind systems so it can be delivered later when those sources aren’t generating. Some experts project that the global demand for lithium-ion batteries may increase tenfold or more in the next decade.

      Given such projections, many researchers are looking for ways to improve the lithium-ion battery technology. Deng and her group aren’t materials scientists, so they don’t focus on making new and better battery chemistries. Instead, their goal is to find a way to lower the high cost of making all of those batteries. And much of the cost of making a lithium-ion battery can be traced to the manufacture of materials used to make one of its two electrodes — the cathode.

      The MIT researchers began their search for cost savings by considering the methods now used to produce cathode materials. The raw materials are typically salts of several metals, including lithium, which provides ions — the electrically charged particles that move when the battery is charged and discharged. The processing technology aims to produce tiny particles, each one made up of a mixture of those ingredients, with the atoms arranged in the specific crystalline structure that will deliver the best performance in the finished battery.

      For the past several decades, companies have manufactured those cathode materials using a two-stage process called coprecipitation. In the first stage, the metal salts — excluding the lithium — are dissolved in water and thoroughly mixed inside a chemical reactor. Chemicals are added to change the acidity (the pH) of the mixture, and particles made up of the combined salts precipitate out of the solution. The particles are then removed, dried, ground up, and put through a sieve.

      A change in pH won’t cause lithium to precipitate, so it is added in the second stage. Solid lithium is ground together with the particles from the first stage until lithium atoms permeate the particles. The resulting material is then heated, or “annealed,” to ensure complete mixing and to achieve the targeted crystalline structure. Finally, the particles go through a “deagglomerator” that separates any particles that have joined together, and the cathode material emerges.

      Coprecipitation produces the needed materials, but the process is time-consuming. The first stage takes about 10 hours, and the second stage requires about 13 hours of annealing at a relatively low temperature (750 degrees Celsius). In addition, to prevent cracking during annealing, the temperature is gradually “ramped” up and down, which takes another 11 hours. The process is thus not only time-consuming but also energy-intensive and costly.

      For the past two years, Deng and her group have been exploring better ways to make the cathode material. “Combustion is very effective at oxidizing things, and the materials for lithium-ion batteries are generally mixtures of metal oxides,” says Deng. That being the case, they thought this could be an opportunity to use a combustion-based process called flame synthesis.

      A new way of making a high-performance cathode material

      The first task for Deng and her team — mechanical engineering postdoc Jianan Zhang, Valerie L. Muldoon ’20, SM ’22, and current graduate students Maanasa Bhat and Chuwei Zhang — was to choose a target material for their study. They decided to focus on a mixture of metal oxides consisting of nickel, cobalt, and manganese plus lithium. Known as “NCM811,” this material is widely used and has been shown to produce cathodes for batteries that deliver high performance; in an electric vehicle, that means a long driving range, rapid discharge and recharge, and a long lifetime. To better define their target, the researchers examined the literature to determine the composition and crystalline structure of NCM811 that has been shown to deliver the best performance as a cathode material.

      They then considered three possible approaches to improving on the coprecipitation process for synthesizing NCM811: They could simplify the system (to cut capital costs), speed up the process, or cut the energy required.

      “Our first thought was, what if we can mix together all of the substances — including the lithium — at the beginning?” says Deng. “Then we would not need to have the two stages” — a clear simplification over coprecipitation.

      Introducing FASP

      One process widely used in the chemical and other industries to fabricate nanoparticles is a type of flame synthesis called flame-assisted spray pyrolysis, or FASP. Deng’s concept for using FASP to make their targeted cathode powders proceeds as follows.

      The precursor materials — the metal salts (including the lithium) — are mixed with water, and the resulting solution is sprayed as fine droplets by an atomizer into a combustion chamber. There, a flame of burning methane heats up the mixture. The water evaporates, leaving the precursor materials to decompose, oxidize, and solidify to form the powder product. The cyclone separates particles of different sizes, and the baghouse filters out those that aren’t useful. The collected particles would then be annealed and deagglomerated.

      To investigate and optimize this concept, the researchers developed a lab-scale FASP setup consisting of a homemade ultrasonic nebulizer, a preheating section, a burner, a filter, and a vacuum pump that withdraws the powders that form. Using that system, they could control the details of the heating process: The preheating section replicates conditions as the material first enters the combustion chamber, and the burner replicates conditions as it passes the flame. That setup allowed the team to explore operating conditions that would give the best results.

      Their experiments showed marked benefits over coprecipitation. The nebulizer breaks up the liquid solution into fine droplets, ensuring atomic-level mixing. The water simply evaporates, so there’s no need to change the pH or to separate the solids from a liquid. As Deng notes, “You just let the gas go, and you’re left with the particles, which is what you want.” With lithium included at the outset, there’s no need for mixing solids with solids, which is neither efficient 
nor effective.

      They could even control the structure, or “morphology,” of the particles that formed. In one series of experiments, they tried exposing the incoming spray to different rates of temperature change over time. They found that the temperature “history” has a direct impact on morphology. With no preheating, the particles burst apart; and with rapid preheating, the particles were hollow. The best outcomes came when they used temperatures ranging from 175-225 C. Experiments with coin-cell batteries (laboratory devices used for testing battery materials) confirmed that by adjusting the preheating temperature, they could achieve a particle morphology that would optimize the performance of their materials.

      Best of all, the particles formed in seconds. Assuming the time needed for conventional annealing and deagglomerating, the new setup could synthesize the finished cathode material in half the total time needed for coprecipitation. Moreover, the first stage of the coprecipitation system is replaced by a far simpler setup — a savings in capital costs.

      “We were very happy,” says Deng. “But then we thought, if we’ve changed the precursor side so the lithium is mixed well with the salts, do we need to have the same process for the second stage? Maybe not!”

      Improving the second stage

      The key time- and energy-consuming step in the second stage is the annealing. In today’s coprecipitation process, the strategy is to anneal at a low temperature for a long time, giving the operator time to manipulate and control the process. But running a furnace for some 20 hours — even at a low temperature — consumes a lot of energy.

      Based on their studies thus far, Deng thought, “What if we slightly increase the temperature but reduce the annealing time by orders of magnitude? Then we could cut energy consumption, and we might still achieve the desired crystal structure.”

      However, experiments at slightly elevated temperatures and short treatment times didn’t bring the results they had hoped for. In transmission electron microscope (TEM) images, the particles that formed had clouds of light-looking nanoscale particles attached to their surfaces. When the researchers performed the same experiments without adding the lithium, those nanoparticles didn’t appear. Based on that and other tests, they concluded that the nanoparticles were pure lithium. So, it seemed like long-duration annealing would be needed to ensure that the lithium made its way inside the particles.

      But they then came up with a different solution to the lithium-distribution problem. They added a small amount — just 1 percent by weight — of an inexpensive compound called urea to their mixture. In TEM images of the particles formed, the “undesirable nanoparticles were largely gone,” says Deng.

      Experiments in the laboratory coin cells showed that the addition of urea significantly altered the response to changes in the annealing temperature. When the urea was absent, raising the annealing temperature led to a dramatic decline in performance of the cathode material that formed. But with the urea present, the performance of the material that formed was unaffected by any temperature change.

      That result meant that — as long as the urea was added with the other precursors — they could push up the temperature, shrink the annealing time, and omit the gradual ramp-up and cool-down process. Further imaging studies confirmed that their approach yields the desired crystal structure and the homogeneous elemental distribution of the cobalt, nickel, manganese, and lithium within the particles. Moreover, in tests of various performance measures, their materials did as well as materials produced by coprecipitation or by other methods using long-time heat treatment. Indeed, the performance was comparable to that of commercial batteries with cathodes made of NCM811.

      So now the long and expensive second stage required in standard coprecipitation could be replaced by just 20 minutes of annealing at about 870 C plus 20 minutes of cooling down at room temperature.

      Theory, continuing work, and planning for scale-up

      While experimental evidence supports their approach, Deng and her group are now working to understand why it works. “Getting the underlying physics right will help us design the process to control the morphology and to scale up the process,” says Deng. And they have a hypothesis for why the lithium nanoparticles in their flame synthesis process end up on the surfaces of the larger particles — and why the presence of urea solves that problem.

      According to their theory, without the added urea, the metal and lithium atoms are initially well-mixed within the droplet. But as heating progresses, the lithium diffuses to the surface and ends up as nanoparticles attached to the solidified particle. As a result, a long annealing process is needed to move the lithium in among the other atoms.

      When the urea is present, it starts out mixed with the lithium and other atoms inside the droplet. As temperatures rise, the urea decomposes, forming bubbles. As heating progresses, the bubbles burst, increasing circulation, which keeps the lithium from diffusing to the surface. The lithium ends up uniformly distributed, so the final heat treatment can be very short.

      The researchers are now designing a system to suspend a droplet of their mixture so they can observe the circulation inside it, with and without the urea present. They’re also developing experiments to examine how droplets vaporize, employing tools and methods they have used in the past to study how hydrocarbons vaporize inside internal combustion engines.

      They also have ideas about how to streamline and scale up their process. In coprecipitation, the first stage takes 10 to 20 hours, so one batch at a time moves on to the second stage to be annealed. In contrast, the novel FASP process generates particles in 20 minutes or less — a rate that’s consistent with continuous processing. In their design for an “integrated synthesis system,” the particles coming out of the baghouse are deposited on a belt that carries them for 10 or 20 minutes through a furnace. A deagglomerator then breaks any attached particles apart, and the cathode powder emerges, ready to be fabricated into a high-performance cathode for a lithium-ion battery. The cathode powders for high-performance lithium-ion batteries would thus be manufactured at unprecedented speed, low cost, and low energy use.

      Deng notes that every component in their integrated system is already used in industry, generally at a large scale and high flow-through rate. “That’s why we see great potential for our technology to be commercialized and scaled up,” she says. “Where our expertise comes into play is in designing the combustion chamber to control the temperature and heating rate so as to produce particles with the desired morphology.” And while a detailed economic analysis has yet to be performed, it seems clear that their technique will be faster, the equipment simpler, and the energy use lower than other methods of manufacturing cathode materials for lithium-ion batteries — potentially a major contribution to the ongoing energy transition.

      This research was supported by the MIT Department of Mechanical Engineering.

      This article appears in the Winter 2023 issue of Energy Futures, the magazine of the MIT Energy Initiative. More

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      in Energy

      How to pull carbon dioxide out of seawater

      by

      As carbon dioxide continues to build up in the Earth’s atmosphere, research teams around the world have spent years seeking ways to remove the gas efficiently from the air. Meanwhile, the world’s number one “sink” for carbon dioxide from the atmosphere is the ocean, which soaks up some 30 to 40 percent of all of the gas produced by human activities.

      Recently, the possibility of removing carbon dioxide directly from ocean water has emerged as another promising possibility for mitigating CO2 emissions, one that could potentially someday even lead to overall net negative emissions. But, like air capture systems, the idea has not yet led to any widespread use, though there are a few companies attempting to enter this area.

      Now, a team of researchers at MIT says they may have found the key to a truly efficient and inexpensive removal mechanism. The findings were reported this week in the journal Energy and Environmental Science, in a paper by MIT professors T. Alan Hatton and Kripa Varanasi, postdoc Seoni Kim, and graduate students Michael Nitzsche, Simon Rufer, and Jack Lake.

      The existing methods for removing carbon dioxide from seawater apply a voltage across a stack of membranes to acidify a feed stream by water splitting. This converts bicarbonates in the water to molecules of CO2, which can then be removed under vacuum. Hatton, who is the Ralph Landau Professor of Chemical Engineering, notes that the membranes are expensive, and chemicals are required to drive the overall electrode reactions at either end of the stack, adding further to the expense and complexity of the processes. “We wanted to avoid the need for introducing chemicals to the anode and cathode half cells and to avoid the use of membranes if at all possible” he says.

      The team came up with a reversible process consisting of membrane-free electrochemical cells. Reactive electrodes are used to release protons to the seawater fed to the cells, driving the release of the dissolved carbon dioxide from the water. The process is cyclic: It first acidifies the water to convert dissolved inorganic bicarbonates to molecular carbon dioxide, which is collected as a gas under vacuum. Then, the water is fed to a second set of cells with a reversed voltage, to recover the protons and turn the acidic water back to alkaline before releasing it back to the sea. Periodically, the roles of the two cells are reversed once one set of electrodes is depleted of protons (during acidification) and the other has been regenerated during alkalization.

      This removal of carbon dioxide and reinjection of alkaline water could slowly start to reverse, at least locally, the acidification of the oceans that has been caused by carbon dioxide buildup, which in turn has threatened coral reefs and shellfish, says Varanasi, a professor of mechanical engineering. The reinjection of alkaline water could be done through dispersed outlets or far offshore to avoid a local spike of alkalinity that could disrupt ecosystems, they say.

      “We’re not going to be able to treat the entire planet’s emissions,” Varanasi says. But the reinjection might be done in some cases in places such as fish farms, which tend to acidify the water, so this could be a way of helping to counter that effect.

      Once the carbon dioxide is removed from the water, it still needs to be disposed of, as with other carbon removal processes. For example, it can be buried in deep geologic formations under the sea floor, or it can be chemically converted into a compound like ethanol, which can be used as a transportation fuel, or into other specialty chemicals. “You can certainly consider using the captured CO2 as a feedstock for chemicals or materials production, but you’re not going to be able to use all of it as a feedstock,” says Hatton. “You’ll run out of markets for all the products you produce, so no matter what, a significant amount of the captured CO2 will need to be buried underground.”

      Initially at least, the idea would be to couple such systems with existing or planned infrastructure that already processes seawater, such as desalination plants. “This system is scalable so that we could integrate it potentially into existing processes that are already processing ocean water or in contact with ocean water,” Varanasi says. There, the carbon dioxide removal could be a simple add-on to existing processes, which already return vast amounts of water to the sea, and it would not require consumables like chemical additives or membranes.

      “With desalination plants, you’re already pumping all the water, so why not co-locate there?” Varanasi says. “A bunch of capital costs associated with the way you move the water, and the permitting, all that could already be taken care of.”

      The system could also be implemented by ships that would process water as they travel, in order to help mitigate the significant contribution of ship traffic to overall emissions. There are already international mandates to lower shipping’s emissions, and “this could help shipping companies offset some of their emissions, and turn ships into ocean scrubbers,” Varanasi says.

      The system could also be implemented at locations such as offshore drilling platforms, or at aquaculture farms. Eventually, it could lead to a deployment of free-standing carbon removal plants distributed globally.

      The process could be more efficient than air-capture systems, Hatton says, because the concentration of carbon dioxide in seawater is more than 100 times greater than it is in air. In direct air-capture systems it is first necessary to capture and concentrate the gas before recovering it. “The oceans are large carbon sinks, however, so the capture step has already kind of been done for you,” he says. “There’s no capture step, only release.” That means the volumes of material that need to be handled are much smaller, potentially simplifying the whole process and reducing the footprint requirements.

      The research is continuing, with one goal being to find an alternative to the present step that requires a vacuum to remove the separated carbon dioxide from the water. Another need is to identify operating strategies to prevent precipitation of minerals that can foul the electrodes in the alkalinization cell, an inherent issue that reduces the overall efficiency in all reported approaches. Hatton notes that significant progress has been made on these issues, but that it is still too early to report on them. The team expects that the system could be ready for a practical demonstration project within about two years.

      “The carbon dioxide problem is the defining problem of our life, of our existence,” Varanasi says. “So clearly, we need all the help we can get.”

      The work was supported by ARPA-E. More