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      Turning carbon dioxide into valuable products

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      Carbon dioxide (CO2) is a major contributor to climate change and a significant product of many human activities, notably industrial manufacturing. A major goal in the energy field has been to chemically convert emitted CO2 into valuable chemicals or fuels. But while CO2 is available in abundance, it has not yet been widely used to generate value-added products. Why not?

      The reason is that CO2 molecules are highly stable and therefore not prone to being chemically converted to a different form. Researchers have sought materials and device designs that could help spur that conversion, but nothing has worked well enough to yield an efficient, cost-effective system.

      Two years ago, Ariel Furst, the Raymond (1921) and Helen St. Laurent Career Development Professor of Chemical Engineering at MIT, decided to try using something different — a material that gets more attention in discussions of biology than of chemical engineering. Already, results from work in her lab suggest that her unusual approach is paying off.

      The stumbling block

      The challenge begins with the first step in the CO2 conversion process. Before being transformed into a useful product, CO2 must be chemically converted into carbon monoxide (CO). That conversion can be encouraged using electrochemistry, a process in which input voltage provides the extra energy needed to make the stable CO2 molecules react. The problem is that achieving the CO2-to-CO conversion requires large energy inputs — and even then, CO makes up only a small fraction of the products that are formed.

      To explore opportunities for improving this process, Furst and her research group focused on the electrocatalyst, a material that enhances the rate of a chemical reaction without being consumed in the process. The catalyst is key to successful operation. Inside an electrochemical device, the catalyst is often suspended in an aqueous (water-based) solution. When an electric potential (essentially a voltage) is applied to a submerged electrode, dissolved CO2 will — helped by the catalyst — be converted to CO.

      But there’s one stumbling block: The catalyst and the CO2 must meet on the surface of the electrode for the reaction to occur. In some studies, the catalyst is dispersed in the solution, but that approach requires more catalyst and isn’t very efficient, according to Furst. “You have to both wait for the diffusion of CO2 to the catalyst and for the catalyst to reach the electrode before the reaction can occur,” she explains. As a result, researchers worldwide have been exploring different methods of “immobilizing” the catalyst on the electrode.

      Connecting the catalyst and the electrode

      Before Furst could delve into that challenge, she needed to decide which of the two types of CO2 conversion catalysts to work with: the traditional solid-state catalyst or a catalyst made up of small molecules. In examining the literature, she concluded that small-molecule catalysts held the most promise. While their conversion efficiency tends to be lower than that of solid-state versions, molecular catalysts offer one important advantage: They can be tuned to emphasize reactions and products of interest.

      Two approaches are commonly used to immobilize small-molecule catalysts on an electrode. One involves linking the catalyst to the electrode by strong covalent bonds — a type of bond in which atoms share electrons; the result is a strong, essentially permanent connection. The other sets up a non-covalent attachment between the catalyst and the electrode; unlike a covalent bond, this connection can easily be broken.

      Neither approach is ideal. In the former case, the catalyst and electrode are firmly attached, ensuring efficient reactions; but when the activity of the catalyst degrades over time (which it will), the electrode can no longer be accessed. In the latter case, a degraded catalyst can be removed; but the exact placement of the small molecules of the catalyst on the electrode can’t be controlled, leading to an inconsistent, often decreasing, catalytic efficiency — and simply increasing the amount of catalyst on the electrode surface without concern for where the molecules are placed doesn’t solve the problem.

      What was needed was a way to position the small-molecule catalyst firmly and accurately on the electrode and then release it when it degrades. For that task, Furst turned to what she and her team regard as a kind of “programmable molecular Velcro”: deoxyribonucleic acid, or DNA.

      Adding DNA to the mix

      Mention DNA to most people, and they think of biological functions in living things. But the members of Furst’s lab view DNA as more than just genetic code. “DNA has these really cool physical properties as a biomaterial that people don’t often think about,” she says. “DNA can be used as a molecular Velcro that can stick things together with very high precision.”

      Furst knew that DNA sequences had previously been used to immobilize molecules on surfaces for other purposes. So she devised a plan to use DNA to direct the immobilization of catalysts for CO2 conversion.

      Her approach depends on a well-understood behavior of DNA called hybridization. The familiar DNA structure is a double helix that forms when two complementary strands connect. When the sequence of bases (the four building blocks of DNA) in the individual strands match up, hydrogen bonds form between complementary bases, firmly linking the strands together.

      Using that behavior for catalyst immobilization involves two steps. First, the researchers attach a single strand of DNA to the electrode. Then they attach a complementary strand to the catalyst that is floating in the aqueous solution. When the latter strand gets near the former, the two strands hybridize; they become linked by multiple hydrogen bonds between properly paired bases. As a result, the catalyst is firmly affixed to the electrode by means of two interlocked, self-assembled DNA strands, one connected to the electrode and the other to the catalyst.

      Better still, the two strands can be detached from one another. “The connection is stable, but if we heat it up, we can remove the secondary strand that has the catalyst on it,” says Furst. “So we can de-hybridize it. That allows us to recycle our electrode surfaces — without having to disassemble the device or do any harsh chemical steps.”

      Experimental investigation

      To explore that idea, Furst and her team — postdocs Gang Fan and Thomas Gill, former graduate student Nathan Corbin PhD ’21, and former postdoc Amruta Karbelkar — performed a series of experiments using three small-molecule catalysts based on porphyrins, a group of compounds that are biologically important for processes ranging from enzyme activity to oxygen transport. Two of the catalysts involve a synthetic porphyrin plus a metal center of either cobalt or iron. The third catalyst is hemin, a natural porphyrin compound used to treat porphyria, a set of disorders that can affect the nervous system. “So even the small-molecule catalysts we chose are kind of inspired by nature,” comments Furst.

      In their experiments, the researchers first needed to modify single strands of DNA and deposit them on one of the electrodes submerged in the solution inside their electrochemical cell. Though this sounds straightforward, it did require some new chemistry. Led by Karbelkar and third-year undergraduate researcher Rachel Ahlmark, the team developed a fast, easy way to attach DNA to electrodes. For this work, the researchers’ focus was on attaching DNA, but the “tethering” chemistry they developed can also be used to attach enzymes (protein catalysts), and Furst believes it will be highly useful as a general strategy for modifying carbon electrodes.

      Once the single strands of DNA were deposited on the electrode, the researchers synthesized complementary strands and attached to them one of the three catalysts. When the DNA strands with the catalyst were added to the solution in the electrochemical cell, they readily hybridized with the DNA strands on the electrode. After half-an-hour, the researchers applied a voltage to the electrode to chemically convert CO2 dissolved in the solution and used a gas chromatograph to analyze the makeup of the gases produced by the conversion.

      The team found that when the DNA-linked catalysts were freely dispersed in the solution, they were highly soluble — even when they included small-molecule catalysts that don’t dissolve in water on their own. Indeed, while porphyrin-based catalysts in solution often stick together, once the DNA strands were attached, that counterproductive behavior was no longer evident.

      The DNA-linked catalysts in solution were also more stable than their unmodified counterparts. They didn’t degrade at voltages that caused the unmodified catalysts to degrade. “So just attaching that single strand of DNA to the catalyst in solution makes those catalysts more stable,” says Furst. “We don’t even have to put them on the electrode surface to see improved stability.” When converting CO2 in this way, a stable catalyst will give a steady current over time. Experimental results showed that adding the DNA prevented the catalyst from degrading at voltages of interest for practical devices. Moreover, with all three catalysts in solution, the DNA modification significantly increased the production of CO per minute.

      Allowing the DNA-linked catalyst to hybridize with the DNA connected to the electrode brought further improvements, even compared to the same DNA-linked catalyst in solution. For example, as a result of the DNA-directed assembly, the catalyst ended up firmly attached to the electrode, and the catalyst stability was further enhanced. Despite being highly soluble in aqueous solutions, the DNA-linked catalyst molecules remained hybridized at the surface of the electrode, even under harsh experimental conditions.

      Immobilizing the DNA-linked catalyst on the electrode also significantly increased the rate of CO production. In a series of experiments, the researchers monitored the CO production rate with each of their catalysts in solution without attached DNA strands — the conventional setup — and then with them immobilized by DNA on the electrode. With all three catalysts, the amount of CO generated per minute was far higher when the DNA-linked catalyst was immobilized on the electrode.

      In addition, immobilizing the DNA-linked catalyst on the electrode greatly increased the “selectivity” in terms of the products. One persistent challenge in using CO2 to generate CO in aqueous solutions is that there is an inevitable competition between the formation of CO and the formation of hydrogen. That tendency was eased by adding DNA to the catalyst in solution — and even more so when the catalyst was immobilized on the electrode using DNA. For both the cobalt-porphyrin catalyst and the hemin-based catalyst, the formation of CO relative to hydrogen was significantly higher with the DNA-linked catalyst on the electrode than in solution. With the iron-porphyrin catalyst they were about the same. “With the iron, it doesn’t matter whether it’s in solution or on the electrode,” Furst explains. “Both of them have selectivity for CO, so that’s good, too.”

      Progress and plans

      Furst and her team have now demonstrated that their DNA-based approach combines the advantages of the traditional solid-state catalysts and the newer small-molecule ones. In their experiments, they achieved the highly efficient chemical conversion of CO2 to CO and also were able to control the mix of products formed. And they believe that their technique should prove scalable: DNA is inexpensive and widely available, and the amount of catalyst required is several orders of magnitude lower when it’s immobilized using DNA.

      Based on her work thus far, Furst hypothesizes that the structure and spacing of the small molecules on the electrode may directly impact both catalytic efficiency and product selectivity. Using DNA to control the precise positioning of her small-molecule catalysts, she plans to evaluate those impacts and then extrapolate design parameters that can be applied to other classes of energy-conversion catalysts. Ultimately, she hopes to develop a predictive algorithm that researchers can use as they design electrocatalytic systems for a wide variety of applications.

      This research was supported by a grant from the MIT Energy Initiative Seed Fund.

      This article appears in the Spring 2022 issue of Energy Futures, the magazine of the MIT Energy Initiative. More

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      in Energy

      Stranded assets could exact steep costs on fossil energy producers and investors

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      A 2021 study in the journal Nature found that in order to avert the worst impacts of climate change, most of the world’s known fossil fuel reserves must remain untapped. According to the study, 90 percent of coal and nearly 60 percent of oil and natural gas must be kept in the ground in order to maintain a 50 percent chance that global warming will not exceed 1.5 degrees Celsius above preindustrial levels.

      As the world transitions away from greenhouse-gas-emitting activities to keep global warming well below 2 C (and ideally 1.5 C) in alignment with the Paris Agreement on climate change, fossil fuel companies and their investors face growing financial risks (known as transition risks), including the prospect of ending up with massive stranded assets. This ongoing transition is likely to significantly scale back fossil fuel extraction and coal-fired power plant operations, exacting steep costs — most notably asset value losses — on fossil-energy producers and shareholders.

      Now, a new study in the journal Climate Change Economics led by researchers at the MIT Joint Program on the Science and Policy of Global Change estimates the current global asset value of untapped fossil fuels through 2050 under four increasingly ambitious climate-policy scenarios. The least-ambitious scenario (“Paris Forever”) assumes that initial Paris Agreement greenhouse gas emissions-reduction pledges are upheld in perpetuity; the most stringent scenario (“Net Zero 2050”) adds coordinated international policy instruments aimed at achieving global net-zero emissions by 2050.

      Powered by the MIT Joint Program’s model of the world economy with detailed representation of the energy sector and energy industry assets over time, the study finds that the global net present value of untapped fossil fuel output through 2050 relative to a reference “No Policy” scenario ranges from $21.5 trillion (Paris Forever) to $30.6 trillion (Net Zero 2050). The estimated global net present value of stranded assets in coal power generation through 2050 ranges from $1.3 to $2.3 trillion.

      “The more stringent the climate policy, the greater the volume of untapped fossil fuels, and hence the higher the potential asset value loss for fossil-fuel owners and investors,” says Henry Chen, a research scientist at the MIT Joint Program and the study’s lead author.

      The global economy-wide analysis presented in the study provides a more fine-grained assessment of stranded assets than those performed in previous studies. Firms and financial institutions may combine the MIT analysis with details on their own investment portfolios to assess their exposure to climate-related transition risk. More

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      in Energy

      Getting the carbon out of India’s heavy industries

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      The world’s third largest carbon emitter after China and the United States, India ranks seventh in a major climate risk index. Unless India, along with the nearly 200 other signatory nations of the Paris Agreement, takes aggressive action to keep global warming well below 2 degrees Celsius relative to preindustrial levels, physical and financial losses from floods, droughts, and cyclones could become more severe than they are today. So, too, could health impacts associated with the hazardous air pollution levels now affecting more than 90 percent of its population.  

      To address both climate and air pollution risks and meet its population’s escalating demand for energy, India will need to dramatically decarbonize its energy system in the coming decades. To that end, its initial Paris Agreement climate policy pledge calls for a reduction in carbon dioxide intensity of GDP by 33-35 percent by 2030 from 2005 levels, and an increase in non-fossil-fuel-based power to about 40 percent of cumulative installed capacity in 2030. At the COP26 international climate change conference, India announced more aggressive targets, including the goal of achieving net-zero emissions by 2070.

      Meeting its climate targets will require emissions reductions in every economic sector, including those where emissions are particularly difficult to abate. In such sectors, which involve energy-intensive industrial processes (production of iron and steel; nonferrous metals such as copper, aluminum, and zinc; cement; and chemicals), decarbonization options are limited and more expensive than in other sectors. Whereas replacing coal and natural gas with solar and wind could lower carbon dioxide emissions in electric power generation and transportation, no easy substitutes can be deployed in many heavy industrial processes that release CO2 into the air as a byproduct.

      However, other methods could be used to lower the emissions associated with these processes, which draw upon roughly 50 percent of India’s natural gas, 25 percent of its coal, and 20 percent of its oil. Evaluating the potential effectiveness of such methods in the next 30 years, a new study in the journal Energy Economics led by researchers at the MIT Joint Program on the Science and Policy of Global Change is the first to explicitly explore emissions-reduction pathways for India’s hard-to-abate sectors.

      Using an enhanced version of the MIT Economic Projection and Policy Analysis (EPPA) model, the study assesses existing emissions levels in these sectors and projects how much they can be reduced by 2030 and 2050 under different policy scenarios. Aimed at decarbonizing industrial processes, the scenarios include the use of subsidies to increase electricity use, incentives to replace coal with natural gas, measures to improve industrial resource efficiency, policies to put a price on carbon, carbon capture and storage (CCS) technology, and hydrogen in steel production.

      The researchers find that India’s 2030 Paris Agreement pledge may still drive up fossil fuel use and associated greenhouse gas emissions, with projected carbon dioxide emissions from hard-to-abate sectors rising by about 2.6 times from 2020 to 2050. But scenarios that also promote electrification, natural gas support, and resource efficiency in hard-to-abate sectors can lower their CO2 emissions by 15-20 percent.

      While appearing to move the needle in the right direction, those reductions are ultimately canceled out by increased demand for the products that emerge from these sectors. So what’s the best path forward?

      The researchers conclude that only the incentive of carbon pricing or the advance of disruptive technology can move hard-to-abate sector emissions below their current levels. To achieve significant emissions reductions, they maintain, the price of carbon must be high enough to make CCS economically viable. In that case, reductions of 80 percent below current levels could be achieved by 2050.

      “Absent major support from the government, India will be unable to reduce carbon emissions in its hard-to-abate sectors in alignment with its climate targets,” says MIT Joint Program deputy director Sergey Paltsev, the study’s lead author. “A comprehensive government policy could provide robust incentives for the private sector in India and generate favorable conditions for foreign investments and technology advances. We encourage decision-makers to use our findings to design efficient pathways to reduce emissions in those sectors, and thereby help lower India’s climate and air pollution-related health risks.” More

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      in Energy

      Making hydrogen power a reality

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      For decades, government and industry have looked to hydrogen as a potentially game-changing tool in the quest for clean energy. As far back as the early days of the Clinton administration, energy sector observers and public policy experts have extolled the virtues of hydrogen — to the point that some people have joked that hydrogen is the energy of the future, “and always will be.”

      Even as wind and solar power have become commonplace in recent years, hydrogen has been held back by high costs and other challenges. But the fuel may finally be poised to have its moment. At the MIT Energy Initiative Spring Symposium — entitled “Hydrogen’s role in a decarbonized energy system” — experts discussed hydrogen production routes, hydrogen consumption markets, the path to a robust hydrogen infrastructure, and policy changes needed to achieve a “hydrogen future.”

      During one panel, “Options for producing low-carbon hydrogen at scale,” four experts laid out existing and planned efforts to leverage hydrogen for decarbonization. 

      “The race is on”

      Huyen N. Dinh, a senior scientist and group manager at the National Renewable Energy Laboratory (NREL), is the director of HydroGEN, a consortium of several U.S. Department of Energy (DOE) national laboratories that accelerates research and development of innovative and advanced water splitting materials and technologies for clean, sustainable, and low-cost hydrogen production.

      For the past 14 years, Dinh has worked on fuel cells and hydrogen production for NREL. “We think that the 2020s is the decade of hydrogen,” she said. Dinh believes that the energy carrier is poised to come into its own over the next few years, pointing to several domestic and international activities surrounding the fuel and citing a Hydrogen Council report that projected the future impacts of hydrogen — including 30 million jobs and $2.5 trillion in global revenue by 2050.

      “Now is the time for hydrogen, and the global race is on,” she said.

      Dinh also explained the parameters of the Hydrogen Shot — the first of the DOE’s “Energy Earthshots” aimed at accelerating breakthroughs for affordable and reliable clean energy solutions. Hydrogen fuel currently costs around $5 per kilogram to produce, and the Hydrogen Shot’s stated goal is to bring that down by 80 percent to $1 per kilogram within a decade.

      The Hydrogen Shot will be facilitated by $9.5 billion in funding for at least four clean hydrogen hubs located in different parts of the United States, as well as extensive research and development, manufacturing, and recycling from last year’s bipartisan infrastructure law. Still, Dinh noted that it took more than 40 years for solar and wind power to become cost competitive, and now industry, government, national lab, and academic leaders are hoping to achieve similar reductions in hydrogen fuel costs over a much shorter time frame. In the near term, she said, stakeholders will need to improve the efficiency, durability, and affordability of hydrogen production through electrolysis (using electricity to split water) using today’s renewable and nuclear power sources. Over the long term, the focus may shift to splitting water more directly through heat or solar energy, she said.

      “The time frame is short, the competition is intense, and a coordinated effort is critical for domestic competitiveness,” Dinh said.

      Hydrogen across continents

      Wambui Mutoru, principal engineer for international commercial development, exploration, and production international at the Norwegian global energy company Equinor, said that hydrogen is an important component in the company’s ambitions to be carbon-neutral by 2050. The company, in collaboration with partners, has several hydrogen projects in the works, and Mutoru laid out the company’s Hydrogen to Humber project in Northern England. Currently, the Humber region emits more carbon dioxide than any other industrial cluster in the United Kingdom — 50 percent more, in fact, than the next-largest carbon emitter.   

      “The ambition here is for us to deploy the world’s first at-scale hydrogen value chain to decarbonize the Humber industrial cluster,” Mutoru said.

      The project consists of three components: a clean hydrogen production facility, an onshore hydrogen and carbon dioxide transmission network, and offshore carbon dioxide transportation and storage operations. Mutoru highlighted the importance of carbon capture and storage in hydrogen production. Equinor, she said, has captured and sequestered carbon offshore for more than 25 years, storing more than 25 million tons of carbon dioxide during that time.

      Mutoru also touched on Equinor’s efforts to build a decarbonized energy hub in the Appalachian region of the United States, covering territory in Ohio, West Virginia, and Pennsylvania. By 2040, she said, the company’s ambition is to produce about 1.5 million tons of clean hydrogen per year in the region — roughly equivalent to 6.8 gigawatts of electricity — while also storing 30 million tons of carbon dioxide.

      Mutoru acknowledged that the biggest challenge facing potential hydrogen producers is the current lack of viable business models. “Resolving that challenge requires cross-industry collaboration, and supportive policy frameworks so that the market for hydrogen can be built and sustained over the long term,” she said.

      Confronting barriers

      Gretchen Baier, executive external strategy and communications leader for Dow, noted that the company already produces hydrogen in multiple ways. For one, Dow operates the world’s largest ethane cracker, in Texas. An ethane cracker heats ethane to break apart molecular bonds to form ethylene, with hydrogen one of the byproducts of the process. Also, Baier showed a slide of the 1891 patent for the electrolysis of brine water, which also produces hydrogen. The company still engages in this practice, but Dow does not have an effective way of utilizing the resulting hydrogen for their own fuel.

      “Just take a moment to think about that,” Baier said. “We’ve been talking about hydrogen production and the cost of it, and this is basically free hydrogen. And it’s still too much of a barrier to somewhat recycle that and use it for ourselves. The environment is clearly changing, and we do have plans for that, but I think that kind of sets some of the challenges that face industry here.”

      However, Baier said, hydrogen is expected to play a significant role in Dow’s future as the company attempts to decarbonize by 2050. The company, she said, plans to optimize hydrogen allocation and production, retrofit turbines for hydrogen fueling, and purchase clean hydrogen. By 2040, Dow expects more than 60 percent of its sites to be hydrogen-ready.

      Baier noted that hydrogen fuel is not a “panacea,” but rather one among many potential contributors as industry attempts to reduce or eliminate carbon emissions in the coming decades. “Hydrogen has an important role, but it’s not the only answer,” she said.

      “This is real”

      Colleen Wright is vice president of corporate strategy for Constellation, which recently separated from Exelon Corporation. (Exelon now owns the former company’s regulated utilities, such as Commonwealth Edison and Baltimore Gas and Electric, while Constellation owns the competitive generation and supply portions of the business.) Wright stressed the advantages of nuclear power in hydrogen production, which she said include superior economics, low barriers to implementation, and scalability.

      “A quarter of emissions in the world are currently from hard-to-decarbonize sectors — the industrial sector, steel making, heavy-duty transportation, aviation,” she said. “These are really challenging decarbonization sectors, and as we continue to expand and electrify, we’re going to need more supply. We’re also going to need to produce clean hydrogen using emissions-free power.”

      “The scale of nuclear power plants is uniquely suited to be able to scale hydrogen production,” Wright added. She mentioned Constellation’s Nine Mile Point site in the State of New York, which received a DOE grant for a pilot program that will see a proton exchange membrane electrolyzer installed at the site.

      “We’re very excited to see hydrogen go from a [research and development] conversation to a commercial conversation,” she said. “We’ve been calling it a little bit of a ‘middle-school dance.’ Everybody is standing around the circle, waiting to see who’s willing to put something at stake. But this is real. We’re not dancing around the edges. There are a lot of people who are big players, who are willing to put skin in the game today.” More

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      in Environment

      Ocean vital signs

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      Without the ocean, the climate crisis would be even worse than it is. Each year, the ocean absorbs billions of tons of carbon from the atmosphere, preventing warming that greenhouse gas would otherwise cause. Scientists estimate about 25 to 30 percent of all carbon released into the atmosphere by both human and natural sources is absorbed by the ocean.

      “But there’s a lot of uncertainty in that number,” says Ryan Woosley, a marine chemist and a principal research scientist in the Department of Earth, Atmospheric and Planetary Sciences (EAPS) at MIT. Different parts of the ocean take in different amounts of carbon depending on many factors, such as the season and the amount of mixing from storms. Current models of the carbon cycle don’t adequately capture this variation.

      To close the gap, Woosley and a team of other MIT scientists developed a research proposal for the MIT Climate Grand Challenges competition — an Institute-wide campaign to catalyze and fund innovative research addressing the climate crisis. The team’s proposal, “Ocean Vital Signs,” involves sending a fleet of sailing drones to cruise the oceans taking detailed measurements of how much carbon the ocean is really absorbing. Those data would be used to improve the precision of global carbon cycle models and improve researchers’ ability to verify emissions reductions claimed by countries.

      “If we start to enact mitigation strategies—either through removing CO2 from the atmosphere or reducing emissions — we need to know where CO2 is going in order to know how effective they are,” says Woosley. Without more precise models there’s no way to confirm whether observed carbon reductions were thanks to policy and people, or thanks to the ocean.

      “So that’s the trillion-dollar question,” says Woosley. “If countries are spending all this money to reduce emissions, is it enough to matter?”

      In February, the team’s Climate Grand Challenges proposal was named one of 27 finalists out of the almost 100 entries submitted. From among this list of finalists, MIT will announce in April the selection of five flagship projects to receive further funding and support.

      Woosley is leading the team along with Christopher Hill, a principal research engineer in EAPS. The team includes physical and chemical oceanographers, marine microbiologists, biogeochemists, and experts in computational modeling from across the department, in addition to collaborators from the Media Lab and the departments of Mathematics, Aeronautics and Astronautics, and Electrical Engineering and Computer Science.

      Today, data on the flux of carbon dioxide between the air and the oceans are collected in a piecemeal way. Research ships intermittently cruise out to gather data. Some commercial ships are also fitted with sensors. But these present a limited view of the entire ocean, and include biases. For instance, commercial ships usually avoid storms, which can increase the turnover of water exposed to the atmosphere and cause a substantial increase in the amount of carbon absorbed by the ocean.

      “It’s very difficult for us to get to it and measure that,” says Woosley. “But these drones can.”

      If funded, the team’s project would begin by deploying a few drones in a small area to test the technology. The wind-powered drones — made by a California-based company called Saildrone — would autonomously navigate through an area, collecting data on air-sea carbon dioxide flux continuously with solar-powered sensors. This would then scale up to more than 5,000 drone-days’ worth of observations, spread over five years, and in all five ocean basins.

      Those data would be used to feed neural networks to create more precise maps of how much carbon is absorbed by the oceans, shrinking the uncertainties involved in the models. These models would continue to be verified and improved by new data. “The better the models are, the more we can rely on them,” says Woosley. “But we will always need measurements to verify the models.”

      Improved carbon cycle models are relevant beyond climate warming as well. “CO2 is involved in so much of how the world works,” says Woosley. “We’re made of carbon, and all the other organisms and ecosystems are as well. What does the perturbation to the carbon cycle do to these ecosystems?”

      One of the best understood impacts is ocean acidification. Carbon absorbed by the ocean reacts to form an acid. A more acidic ocean can have dire impacts on marine organisms like coral and oysters, whose calcium carbonate shells and skeletons can dissolve in the lower pH. Since the Industrial Revolution, the ocean has become about 30 percent more acidic on average.

      “So while it’s great for us that the oceans have been taking up the CO2, it’s not great for the oceans,” says Woosley. “Knowing how this uptake affects the health of the ocean is important as well.” More

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      in Environment

      MIT entrepreneurs think globally, act locally

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      Born and raised amid the natural beauty of the Dominican Republic, Andrés Bisonó León feels a deep motivation to help solve a problem that has been threatening the Caribbean island nation’s tourism industry, its economy, and its people.

      As Bisonó León discussed with his long-time friend and mentor, the Walter M. May and A. Hazel May Professor of Mechanical Engineering (MechE) Alexander Slocum Sr., ugly mats of toxic sargassum seaweed have been encroaching on the Dominican Republic’s pristine beaches and other beaches in the Caribbean region, and public and private organizations have fought a losing battle using expensive, environmentally damaging methods to clean it up. Slocum, who was on the U.S. Department of Energy’s Deepwater Horizon team, has extensive experience with systems that operate in the ocean.

      “In the last 10 years,” says Bisonó León, now an MBA candidate in the MIT Sloan School of Management, “sargassum, a toxic seaweed invasion, has cost the Caribbean as much as $120 million a year in cleanup and has meant a 30 to 35 percent tourism reduction, affecting not only the tourism industry, but also the environment, marine life, local economies, and human health.”

      One of Bisonó León’s discussions with Slocum took place within earshot of MechE alumnus Luke Gray ’18, SM ’20, who had worked with Slocum on other projects and was at the time was about to begin his master’s program.

      “Professor Slocum and Andrés happened to be discussing the sargassum problem in Andrés’ home country,” Gray says. “A week later I was on a plane to the DR to collect sargassum samples and survey the problem in Punta Cana. When I returned, my master’s program was underway, and I already had my thesis project!”

      Gray also had started a working partnership with Bisonó León, which both say proceeded seamlessly right from the first moment.

      “I feel that Luke right away understood the magnitude of the problem and the value we could create in the Dominican Republic and across the Caribbean by teaming up,” Bisonó León says.

      Both Bisonó León and Gray also say they felt a responsibility to work toward helping the global environment.

      “All of my major projects up until now have involved machines for climate restoration and/or adaptation,” says Gray.

      The technologies Bisonó León and Gray arrived at after 18 months of R&D were designed to provide solutions both locally and globally.

      Their Littoral Collection Module (LCM) skims sargassum seaweed off the surface of the water with nets that can be mounted on any boat. The device sits across the boat, with two large hoops holding the nets open, one on each side. As the boat travels forward, it cuts through the seaweed, which flows to the sides of the vessel and through the hoops into the nets. Effective at sweeping the seaweed from the water, the device can be employed by anyone with a boat, including local fishermen whose livelihoods have been disrupted by the seaweed’s damaging effect on tourism and the local economy.

      The sargassum can then be towed out to sea, where Bisonó León’s and Gray’s second technology can come into play. By pumping the seaweed into very deep water, where it then sinks to the bottom of the ocean, the carbon in the seaweed can be sequestered. Other methods for disposing of the seaweed generally involve putting it into landfills, where it emits greenhouse gases such as methane and carbon dioxide as it breaks down. Although some seaweed can be put to other uses, including as fertilizer, sargassum has been found to contain hard-to-remove toxic substances such as arsenic and heavy metals.

      In spring 2020, Bisonó León and Gray formed a company, SOS (Sargassum Ocean Sequestration) Carbon.

      Bisonó León says he comes from a long line of entrepreneurs who often expressed much commitment to social impact. His family has been involved in several different industries, his grandfather and great uncles having opened the first cigar factory in the Dominican Republic in 1903.

      Gray says internships with startup companies and the undergraduate projects he did with Slocum developed his interest in entrepreneurship, and his involvement with the sargassum problem only reinforced that inclination. During his master’s program, he says he became “obsessed” with finding a solution.

      “Professor Slocum let me think extremely big, and so it was almost inevitable that the distillation of our two years of work would continue in some form, and starting a company happened to be the right path. My master’s experience of taking an essentially untouched problem like sargassum and then one year later designing, building, and sending 15,000 pounds of custom equipment to test for three months on a Dominican Navy ship made me realize I had discovered a recipe I could repeat — and machine design had become my core competency,” Gray says.

      During the initial research and development of their technologies, Bisonó León and Gray raised $258,000 from 20 different organizations. Between June and December 2021, they succeeded in removing 3.5 million pounds of sargassum and secured contracts with Grupo Puntacana, which operates several tourist resorts, and with other hotels such as Club Med in Punta Cana. The company subcontracts with the association of fishermen in Punta Cana, employing 15 fishermen who operate LCMs and training 35 others to join as the operation expands.

      Their success so far demonstrates “’mens et manus’ at work,” says Slocum, referring to MIT’s motto, which is Latin for “mind and hand.” “Geeks hear about a very real problem that affects very real people who have no other option for their livelihoods, and they respond by inventing a solution so elegant that it can be readily deployed by those most hurt by the problem to address the problem.

      “The team was always focused on the numbers, from physics to finance, and did not let hype or doubts deter their determination to rationally solve this huge problem.”

      Slocum says he could predict Bisonó León and Gray would work well together “because they started out as good, smart people with complementary skills whose hearts and minds were in the right place.”

      “We are working on having a global impact to reduce millions of tons of CO2 per year,” says Bisonó León. “With training from Sloan and cross-disciplinary collaborative spirit, we will be able to further expand environmental and social impact platforms much needed in the Caribbean to be able to drive real change regionally and globally.”

      “I hope SOS Carbon can serve as a model and inspire similar entrepreneurial efforts,” Gray says. More

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      in Environment

      Students dive into research with the MIT Climate and Sustainability Consortium

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      Throughout the fall 2021 semester, the MIT Climate and Sustainability Consortium (MCSC) supported several research projects with a climate-and-sustainability topic related to the consortium, through the MIT Undergraduate Research Opportunities Program (UROP). These students, who represent a range of disciplines, had the opportunity to work with MCSC Impact Fellows on topics related directly to the ongoing work and collaborations with MCSC member companies and the broader MIT community, from carbon capture to value-chain resilience to biodegradables. Many of these students are continuing their work this spring semester.

      Hannah Spilman, who is studying chemical engineering, worked with postdoc Glen Junor, an MCSC Impact Fellow, to investigate carbon capture, utilization, and storage (CCUS), with the goal of facilitating CCUS on a gigaton scale, a much larger capacity than what currently exists. “Scientists agree CCUS will be an important tool in combating climate change, but the largest CCUS facility only captures CO2 on a megaton scale, and very few facilities are actually operating,” explains Spilman. 

      Throughout her UROP, she worked on analyzing the currently deployed technology in the CCUS field, using National Carbon Capture Center post-combustion project reports to synthesize the results and outline those technologies. Examining projects like the RTI-NAS experiment, which showcased innovation with carbon capture technology, was especially helpful. “We must first understand where we are, and as we continue to conduct analyses, we will be able to understand the field’s current state and path forward,” she concludes.

      Fellow chemical engineering students Claire Kim and Alfonso Restrepo are working with postdoc and MCSC Impact Fellow Xiangkun (Elvis) Cao, also on investigating CCUS technology. Kim’s focus is on life cycle assessment (LCA), while Restrepo’s focus is on techno-economic assessment (TEA). They have been working together to use the two tools to evaluate multiple CCUS technologies. While LCA and TEA are not new tools themselves, their application in CCUS has not been comprehensively defined and described. “CCUS can play an important role in the flexible, low-carbon energy systems,” says Kim, which was part of the motivation behind her project choice.

      Through TEA, Restrepo has been investigating how various startups and larger companies are incorporating CCUS technology in their processes. “In order to reduce CO2 emissions before it’s too late to act, there is a strong need for resources that effectively evaluate CCUS technology, to understand the effectiveness and viability of emerging technology for future implementation,” he explains. For their next steps, Kim and Restrepo will apply LCA and TEA to the analysis of a specific capture (for example, direct ocean capture) or conversion (for example, CO2-to-fuel conversion) process​ in CCUS.

      Cameron Dougal, a first-year student, and James Santoro, studying management, both worked with postdoc and MCSC Impact Fellow Paloma Gonzalez-Rojas on biodegradable materials. Dougal explored biodegradable packaging film in urban systems. “I have had a longstanding interest in sustainability, with a newer interest in urban planning and design, which motivated me to work on this project,” Dougal says. “Bio-based plastics are a promising step for the future.”

      Dougal spent time conducting internet and print research, as well as speaking with faculty on their relevant work. From these efforts, Dougal has identified important historical context for the current recycling landscape — as well as key case studies and cities around the world to explore further. In addition to conducting more research, Dougal plans to create a summary and statistic sheet.

      Santoro dove into the production angle, working on evaluating the economic viability of the startups that are creating biodegradable materials. “Non-renewable plastics (created with fossil fuels) continue to pollute and irreparably damage our environment,” he says. “As we look for innovative solutions, a key question to answer is how can we determine a more effective way to evaluate the economic viability and probability of success for new startups and technologies creating biodegradable plastics?” The project aims to develop an effective framework to begin to answer this.

      At this point, Santoro has been understanding the overall ecosystem, understanding how these biodegradable materials are developed, and analyzing the economics side of things. He plans to have conversations with company founders, investors, and experts, and identify major challenges for biodegradable technology startups in creating high performance products with attractive unit economics. There is also still a lot to research about new technologies and trends in the industry, the profitability of different products, as well as specific individual companies doing this type of work.

      Tess Buchanan, who is studying materials science and engineering, is working with Katharina Fransen and Sarah Av-Ron, MIT graduate students in the Department of Chemical Engineering, and principal investigator Professor Bradley Olsen, to also explore biodegradables by looking into their development from biomass “This is critical work, given the current plastics sustainability crisis, and the potential of bio-based polymers,” Buchanan says.

      The objective of the project is to explore new sustainable polymers through a biodegradation assay using clear zone growth analysis to yield degradation rates. For next steps, Buchanan is diving into synthesis expansion and using machine learning to understand the relationship between biodegradation and polymer chemistry.

      Kezia Hector, studying chemical engineering, and Tamsin Nottage, a first-year student, working with postdoc and MCSC Impact Fellow Sydney Sroka, explored advancing and establishing sustainable solutions for value chain resilience. Hector’s focus was understanding how wildfires can affect supply chains, specifically identifying sources of economic loss. She reviewed academic literature and news articles, and looked at the Amazon, California, Siberia, and Washington, finding that wildfires cause millions of dollars in damage every year and impact supply chains by cutting off or slowing down freight activity. She will continue to identify ways to make supply chains more resilient and sustainable.

      Nottage focused on the economic impact of typhoons, closely studying Typhoon Mangkhut, a powerful and catastrophic tropical cyclone that caused extensive damages of $593 million in Guam, the Philippines, and South China in September 2018. “As a Bahamian, I’ve witnessed the ferocity of hurricanes and challenges of rebuilding after them,” says Nottage. “I used this project to identify the tropical cyclones that caused the most extensive damage for further investigation.”She compiled the causes of damage and their costs to inform targets of supply chain resiliency reform (shipping, building materials, power supply, etc.). As a next step, Nottage will focus on modeling extreme events like Mangkunt to develop frameworks that companies can learn from and utilize to build more sustainable supply chains in the future.

      Ellie Vaserman, a first-year student working with postdoc and MCSC Impact Fellow Poushali Maji, also explored a topic related to value chains: unlocking circularity across the entire value chain through quality improvement, inclusive policy, and behavior to improve materials recovery. Specifically, her objectives have been to learn more about methods of chemolysis and the viability of their products, to compare methods of chemical recycling of polyethylene terephthalate (PET) using quantitative metrics, and to design qualitative visuals to make the steps in PET chemical recycling processes more understandable.

      To do so, she conducted a literature review to identify main methods of chemolysis that are utilized in the field (and collect data about these methods) and created graphics for some of the more common processes. Moving forward, she hopes to compare the processes using other metrics and research the energy intensity of the monomer purification processes.

      The work of these students, as well as many others, continued over MIT’s Independent Activities Period in January. More

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      in Environment

      Q&A: More-sustainable concrete with machine learning

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      As a building material, concrete withstands the test of time. Its use dates back to early civilizations, and today it is the most popular composite choice in the world. However, it’s not without its faults. Production of its key ingredient, cement, contributes 8-9 percent of the global anthropogenic CO2 emissions and 2-3 percent of energy consumption, which is only projected to increase in the coming years. With aging United States infrastructure, the federal government recently passed a milestone bill to revitalize and upgrade it, along with a push to reduce greenhouse gas emissions where possible, putting concrete in the crosshairs for modernization, too.

      Elsa Olivetti, the Esther and Harold E. Edgerton Associate Professor in the MIT Department of Materials Science and Engineering, and Jie Chen, MIT-IBM Watson AI Lab research scientist and manager, think artificial intelligence can help meet this need by designing and formulating new, more sustainable concrete mixtures, with lower costs and carbon dioxide emissions, while improving material performance and reusing manufacturing byproducts in the material itself. Olivetti’s research improves environmental and economic sustainability of materials, and Chen develops and optimizes machine learning and computational techniques, which he can apply to materials reformulation. Olivetti and Chen, along with their collaborators, have recently teamed up for an MIT-IBM Watson AI Lab project to make concrete more sustainable for the benefit of society, the climate, and the economy.

      Q: What applications does concrete have, and what properties make it a preferred building material?

      Olivetti: Concrete is the dominant building material globally with an annual consumption of 30 billion metric tons. That is over 20 times the next most produced material, steel, and the scale of its use leads to considerable environmental impact, approximately 5-8 percent of global greenhouse gas (GHG) emissions. It can be made locally, has a broad range of structural applications, and is cost-effective. Concrete is a mixture of fine and coarse aggregate, water, cement binder (the glue), and other additives.

      Q: Why isn’t it sustainable, and what research problems are you trying to tackle with this project?

      Olivetti: The community is working on several ways to reduce the impact of this material, including alternative fuels use for heating the cement mixture, increasing energy and materials efficiency and carbon sequestration at production facilities, but one important opportunity is to develop an alternative to the cement binder.

      While cement is 10 percent of the concrete mass, it accounts for 80 percent of the GHG footprint. This impact is derived from the fuel burned to heat and run the chemical reaction required in manufacturing, but also the chemical reaction itself releases CO2 from the calcination of limestone. Therefore, partially replacing the input ingredients to cement (traditionally ordinary Portland cement or OPC) with alternative materials from waste and byproducts can reduce the GHG footprint. But use of these alternatives is not inherently more sustainable because wastes might have to travel long distances, which adds to fuel emissions and cost, or might require pretreatment processes. The optimal way to make use of these alternate materials will be situation-dependent. But because of the vast scale, we also need solutions that account for the huge volumes of concrete needed. This project is trying to develop novel concrete mixtures that will decrease the GHG impact of the cement and concrete, moving away from the trial-and-error processes towards those that are more predictive.

      Chen: If we want to fight climate change and make our environment better, are there alternative ingredients or a reformulation we could use so that less greenhouse gas is emitted? We hope that through this project using machine learning we’ll be able to find a good answer.

      Q: Why is this problem important to address now, at this point in history?

      Olivetti: There is urgent need to address greenhouse gas emissions as aggressively as possible, and the road to doing so isn’t necessarily straightforward for all areas of industry. For transportation and electricity generation, there are paths that have been identified to decarbonize those sectors. We need to move much more aggressively to achieve those in the time needed; further, the technological approaches to achieve that are more clear. However, for tough-to-decarbonize sectors, such as industrial materials production, the pathways to decarbonization are not as mapped out.

      Q: How are you planning to address this problem to produce better concrete?

      Olivetti: The goal is to predict mixtures that will both meet performance criteria, such as strength and durability, with those that also balance economic and environmental impact. A key to this is to use industrial wastes in blended cements and concretes. To do this, we need to understand the glass and mineral reactivity of constituent materials. This reactivity not only determines the limit of the possible use in cement systems but also controls concrete processing, and the development of strength and pore structure, which ultimately control concrete durability and life-cycle CO2 emissions.

      Chen: We investigate using waste materials to replace part of the cement component. This is something that we’ve hypothesized would be more sustainable and economic — actually waste materials are common, and they cost less. Because of the reduction in the use of cement, the final concrete product would be responsible for much less carbon dioxide production. Figuring out the right concrete mixture proportion that makes endurable concretes while achieving other goals is a very challenging problem. Machine learning is giving us an opportunity to explore the advancement of predictive modeling, uncertainty quantification, and optimization to solve the issue. What we are doing is exploring options using deep learning as well as multi-objective optimization techniques to find an answer. These efforts are now more feasible to carry out, and they will produce results with reliability estimates that we need to understand what makes a good concrete.

      Q: What kinds of AI and computational techniques are you employing for this?

      Olivetti: We use AI techniques to collect data on individual concrete ingredients, mix proportions, and concrete performance from the literature through natural language processing. We also add data obtained from industry and/or high throughput atomistic modeling and experiments to optimize the design of concrete mixtures. Then we use this information to develop insight into the reactivity of possible waste and byproduct materials as alternatives to cement materials for low-CO2 concrete. By incorporating generic information on concrete ingredients, the resulting concrete performance predictors are expected to be more reliable and transformative than existing AI models.

      Chen: The final objective is to figure out what constituents, and how much of each, to put into the recipe for producing the concrete that optimizes the various factors: strength, cost, environmental impact, performance, etc. For each of the objectives, we need certain models: We need a model to predict the performance of the concrete (like, how long does it last and how much weight does it sustain?), a model to estimate the cost, and a model to estimate how much carbon dioxide is generated. We will need to build these models by using data from literature, from industry, and from lab experiments.

      We are exploring Gaussian process models to predict the concrete strength, going forward into days and weeks. This model can give us an uncertainty estimate of the prediction as well. Such a model needs specification of parameters, for which we will use another model to calculate. At the same time, we also explore neural network models because we can inject domain knowledge from human experience into them. Some models are as simple as multi-layer perceptions, while some are more complex, like graph neural networks. The goal here is that we want to have a model that is not only accurate but also robust — the input data is noisy, and the model must embrace the noise, so that its prediction is still accurate and reliable for the multi-objective optimization.

      Once we have built models that we are confident with, we will inject their predictions and uncertainty estimates into the optimization of multiple objectives, under constraints and under uncertainties.

      Q: How do you balance cost-benefit trade-offs?

      Chen: The multiple objectives we consider are not necessarily consistent, and sometimes they are at odds with each other. The goal is to identify scenarios where the values for our objectives cannot be further pushed simultaneously without compromising one or a few. For example, if you want to further reduce the cost, you probably have to suffer the performance or suffer the environmental impact. Eventually, we will give the results to policymakers and they will look into the results and weigh the options. For example, they may be able to tolerate a slightly higher cost under a significant reduction in greenhouse gas. Alternatively, if the cost varies little but the concrete performance changes drastically, say, doubles or triples, then this is definitely a favorable outcome.

      Q: What kinds of challenges do you face in this work?

      Chen: The data we get either from industry or from literature are very noisy; the concrete measurements can vary a lot, depending on where and when they are taken. There are also substantial missing data when we integrate them from different sources, so, we need to spend a lot of effort to organize and make the data usable for building and training machine learning models. We also explore imputation techniques that substitute missing features, as well as models that tolerate missing features, in our predictive modeling and uncertainty estimate.

      Q: What do you hope to achieve through this work?

      Chen: In the end, we are suggesting either one or a few concrete recipes, or a continuum of recipes, to manufacturers and policymakers. We hope that this will provide invaluable information for both the construction industry and for the effort of protecting our beloved Earth.

      Olivetti: We’d like to develop a robust way to design cements that make use of waste materials to lower their CO2 footprint. Nobody is trying to make waste, so we can’t rely on one stream as a feedstock if we want this to be massively scalable. We have to be flexible and robust to shift with feedstocks changes, and for that we need improved understanding. Our approach to develop local, dynamic, and flexible alternatives is to learn what makes these wastes reactive, so we know how to optimize their use and do so as broadly as possible. We do that through predictive model development through software we have developed in my group to automatically extract data from literature on over 5 million texts and patents on various topics. We link this to the creative capabilities of our IBM collaborators to design methods that predict the final impact of new cements. If we are successful, we can lower the emissions of this ubiquitous material and play our part in achieving carbon emissions mitigation goals.

      Other researchers involved with this project include Stefanie Jegelka, the X-Window Consortium Career Development Associate Professor in the MIT Department of Electrical Engineering and Computer Science; Richard Goodwin, IBM principal researcher; Soumya Ghosh, MIT-IBM Watson AI Lab research staff member; and Kristen Severson, former research staff member. Collaborators included Nghia Hoang, former research staff member with MIT-IBM Watson AI Lab and IBM Research; and Jeremy Gregory, research scientist in the MIT Department of Civil and Environmental Engineering and executive director of the MIT Concrete Sustainability Hub.

      This research is supported by the MIT-IBM Watson AI Lab. More