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      in Environment

      Concrete’s role in reducing building and pavement emissions

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      Encountering concrete is a common, even routine, occurrence. And that’s exactly what makes concrete exceptional.

      As the most consumed material after water, concrete is indispensable to the many essential systems — from roads to buildings — in which it is used.

      But due to its extensive use, concrete production also contributes to around 1 percent of emissions in the United States and remains one of several carbon-intensive industries globally. Tackling climate change, then, will mean reducing the environmental impacts of concrete, even as its use continues to increase.

      In a new paper in the Proceedings of the National Academy of Sciences, a team of current and former researchers at the MIT Concrete Sustainability Hub (CSHub) outlines how this can be achieved.

      They present an extensive life-cycle assessment of the building and pavements sectors that estimates how greenhouse gas (GHG) reduction strategies — including those for concrete and cement — could minimize the cumulative emissions of each sector and how those reductions would compare to national GHG reduction targets. 

      The team found that, if reduction strategies were implemented, the emissions for pavements and buildings between 2016 and 2050 could fall by up to 65 percent and 57 percent, respectively, even if concrete use accelerated greatly over that period. These are close to U.S. reduction targets set as part of the Paris Climate Accords. The solutions considered would also enable concrete production for both sectors to attain carbon neutrality by 2050.

      Despite continued grid decarbonization and increases in fuel efficiency, they found that the vast majority of the GHG emissions from new buildings and pavements during this period would derive from operational energy consumption rather than so-called embodied emissions — emissions from materials production and construction.

      Sources and solutions

      The consumption of concrete, due to its versatility, durability, constructability, and role in economic development, has been projected to increase around the world.

      While it is essential to consider the embodied impacts of ongoing concrete production, it is equally essential to place these initial impacts in the context of the material’s life cycle.

      Due to concrete’s unique attributes, it can influence the long-term sustainability performance of the systems in which it is used. Concrete pavements, for instance, can reduce vehicle fuel consumption, while concrete structures can endure hazards without needing energy- and materials-intensive repairs.

      Concrete’s impacts, then, are as complex as the material itself — a carefully proportioned mixture of cement powder, water, sand, and aggregates. Untangling concrete’s contribution to the operational and embodied impacts of buildings and pavements is essential for planning GHG reductions in both sectors.

      Set of scenarios

      In their paper, CSHub researchers forecast the potential greenhouse gas emissions from the building and pavements sectors as numerous emissions reduction strategies were introduced between 2016 and 2050.

      Since both of these sectors are immense and rapidly evolving, modeling them required an intricate framework.

      “We don’t have details on every building and pavement in the United States,” explains Randolph Kirchain, a research scientist at the Materials Research Laboratory and co-director of CSHub.

      “As such, we began by developing reference designs, which are intended to be representative of current and future buildings and pavements. These were adapted to be appropriate for 14 different climate zones in the United States and then distributed across the U.S. based on data from the U.S. Census and the Federal Highway Administration”

      To reflect the complexity of these systems, their models had to have the highest resolutions possible.

      “In the pavements sector, we collected the current stock of the U.S. network based on high-precision 10-mile segments, along with the surface conditions, traffic, thickness, lane width, and number of lanes for each segment,” says Hessam AzariJafari, a postdoc at CSHub and a co-author on the paper.

      “To model future paving actions over the analysis period, we assumed four climate conditions; four road types; asphalt, concrete, and composite pavement structures; as well as major, minor, and reconstruction paving actions specified for each climate condition.”

      Using this framework, they analyzed a “projected” and an “ambitious” scenario of reduction strategies and system attributes for buildings and pavements over the 34-year analysis period. The scenarios were defined by the timing and intensity of GHG reduction strategies.

      As its name might suggest, the projected scenario reflected current trends. For the building sector, solutions encompassed expected grid decarbonization and improvements to building codes and energy efficiency that are currently being implemented across the country. For pavements, the sole projected solution was improvements to vehicle fuel economy. That’s because as vehicle efficiency continues to increase, excess vehicle emissions due to poor road quality will also decrease.

      Both the projected scenarios for buildings and pavements featured the gradual introduction of low-carbon concrete strategies, such as recycled content, carbon capture in cement production, and the use of captured carbon to produce aggregates and cure concrete.

      “In the ambitious scenario,” explains Kirchain, “we went beyond projected trends and explored reasonable changes that exceed current policies and [industry] commitments.”

      Here, the building sector strategies were the same, but implemented more aggressively. The pavements sector also abided by more aggressive targets and incorporated several novel strategies, including investing more to yield smoother roads, selectively applying concrete overlays to produce stiffer pavements, and introducing more reflective pavements — which can change the Earth’s energy balance by sending more energy out of the atmosphere.

      Results

      As the grid becomes greener and new homes and buildings become more efficient, many experts have predicted the operational impacts of new construction projects to shrink in comparison to their embodied emissions.

      “What our life-cycle assessment found,” says Jeremy Gregory, the executive director of the MIT Climate Consortium and the lead author on the paper, “is that [this prediction] isn’t necessarily the case.”

      “Instead, we found that more than 80 percent of the total emissions from new buildings and pavements between 2016 and 2050 would derive from their operation.”

      In fact, the study found that operations will create the majority of emissions through 2050 unless all energy sources — electrical and thermal — are carbon-neutral by 2040. This suggests that ambitious interventions to the electricity grid and other sources of operational emissions can have the greatest impact.

      Their predictions for emissions reductions generated additional insights.  

      For the building sector, they found that the projected scenario would lead to a reduction of 49 percent compared to 2016 levels, and that the ambitious scenario provided a 57 percent reduction.

      As most buildings during the analysis period were existing rather than new, energy consumption dominated emissions in both scenarios. Consequently, decarbonizing the electricity grid and improving the efficiency of appliances and lighting led to the greatest improvements for buildings, they found.

      In contrast to the building sector, the pavements scenarios had a sizeable gulf between outcomes: the projected scenario led to only a 14 percent reduction while the ambitious scenario had a 65 percent reduction — enough to meet U.S. Paris Accord targets for that sector. This gulf derives from the lack of GHG reduction strategies being pursued under current projections.

      “The gap between the pavement scenarios shows that we need to be more proactive in managing the GHG impacts from pavements,” explains Kirchain. “There is tremendous potential, but seeing those gains requires action now.”

      These gains from both ambitious scenarios could occur even as concrete use tripled over the analysis period in comparison to the projected scenarios — a reflection of not only concrete’s growing demand but its potential role in decarbonizing both sectors.

      Though only one of their reduction scenarios (the ambitious pavement scenario) met the Paris Accord targets, that doesn’t preclude the achievement of those targets: many other opportunities exist.

      “In this study, we focused on mainly embodied reductions for concrete,” explains Gregory. “But other construction materials could receive similar treatment.

      “Further reductions could also come from retrofitting existing buildings and by designing structures with durability, hazard resilience, and adaptability in mind in order to minimize the need for reconstruction.”

      This study answers a paradox in the field of sustainability. For the world to become more equitable, more development is necessary. And yet, that very same development may portend greater emissions.

      The MIT team found that isn’t necessarily the case. Even as America continues to use more concrete, the benefits of the material itself and the interventions made to it can make climate targets more achievable.

      The MIT Concrete Sustainability Hub is a team of researchers from several departments across MIT working on concrete and infrastructure science, engineering, and economics. Its research is supported by the Portland Cement Association and the Ready Mixed Concrete Research and Education Foundation. More

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      in Energy

      3 Questions: Daniel Cohn on the benefits of high-efficiency, flexible-fuel engines for heavy-duty trucking

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      The California Air Resources Board has adopted a regulation that requires truck and engine manufacturers to reduce the nitrogen oxide (NOx) emissions from new heavy-duty trucks by 90 percent starting in 2027. NOx from heavy-duty trucks is one of the main sources of air pollution, creating smog and threatening respiratory health. This regulation requires the largest air pollution cuts in California in more than a decade. How can manufacturers achieve this aggressive goal efficiently and affordably?

      Daniel Cohn, a research scientist at the MIT Energy Initiative, and Leslie Bromberg, a principal research scientist at the MIT Plasma Science and Fusion Center, have been working on a high-efficiency, gasoline-ethanol engine that is cleaner and more cost-effective than existing diesel engine technologies. Here, Cohn explains the flexible-fuel engine approach and why it may be the most realistic solution — in the near term — to help California meet its stringent vehicle emission reduction goals. The research was sponsored by the Arthur Samberg MIT Energy Innovation fund.

      Q. How does your high-efficiency, flexible-fuel gasoline engine technology work?

      A. Our goal is to provide an affordable solution for heavy-duty vehicle (HDV) engines to emit low levels of nitrogen oxide (NOx) emissions that would meet California’s NOx regulations, while also quick-starting gasoline-consumption reductions in a substantial fraction of the HDV fleet.

      Presently, large trucks and other HDVs generally use diesel engines. The main reason for this is because of their high efficiency, which reduces fuel cost — a key factor for commercial trucks (especially long-haul trucks) because of the large number of miles that are driven. However, the NOx emissions from these diesel-powered vehicles are around 10 times greater than those from spark-ignition engines powered by gasoline or ethanol.

      Spark-ignition gasoline engines are primarily used in cars and light trucks (light-duty vehicles), which employ a three-way catalyst exhaust treatment system (generally referred to as a catalytic converter) that reduces vehicle NOx emissions by at least 98 percent and at a modest cost. The use of this highly effective exhaust treatment system is enabled by the capability of spark-ignition engines to be operated at a stoichiometric air/fuel ratio (where the amount of air matches what is needed for complete combustion of the fuel).

      Diesel engines do not operate with stoichiometric air/fuel ratios, making it much more difficult to reduce NOx emissions. Their state-of-the-art exhaust treatment system is much more complex and expensive than catalytic converters, and even with it, vehicles produce NOx emissions around 10 times higher than spark-ignition engine vehicles. Consequently, it is very challenging for diesel engines to further reduce their NOx emissions to meet the new California regulations.

      Our approach uses spark-ignition engines that can be powered by gasoline, ethanol, or mixtures of gasoline and ethanol as a substitute for diesel engines in HDVs. Gasoline has the attractive feature of being widely available and having a comparable or lower cost than diesel fuel. In addition, presently available ethanol in the U.S. produces up to 40 percent less greenhouse gas (GHG) emissions than diesel fuel or gasoline and has a widely available distribution system.

      To make gasoline- and/or ethanol-powered spark-ignition engine HDVs attractive for widespread HDV applications, we developed ways to make spark-ignition engines more efficient, so their fuel costs are more palatable to owners of heavy-duty trucks. Our approach provides diesel-like high efficiency and high power in gasoline-powered engines by using various methods to prevent engine knock (unwanted self-ignition that can damage the engine) in spark-ignition gasoline engines. This enables greater levels of turbocharging and use of higher engine compression ratios. These features provide high efficiency, comparable to that provided by diesel engines. Plus, when the engine is powered by ethanol, the required knock resistance is provided by the intrinsic high knock resistance of the fuel itself. 

      Q. What are the major challenges to implementing your technology in California?

      A. California has always been the pioneer in air pollutant control, with states such as Washington, Oregon, and New York often following suit. As the most populous state, California has a lot of sway — it’s a trendsetter. What happens in California has an impact on the rest of the United States.

      The main challenge to implementation of our technology is the argument that a better internal combustion engine technology is not needed because battery-powered HDVs — particularly long-haul trucks — can play the required role in reducing NOx and GHG emissions by 2035. We think that substantial market penetration of battery electric vehicles (BEV) in this vehicle sector will take a considerably longer time. In contrast to light-duty vehicles, there has been very little penetration of battery power into the HDV fleet, especially in long-haul trucks, which are the largest users of diesel fuel. One reason for this is that long-haul trucks using battery power face the challenge of reduced cargo capability due to substantial battery weight. Another challenge is the substantially longer charging time for BEVs compared to that of most present HDVs.

      Hydrogen-powered trucks using fuel cells have also been proposed as an alternative to BEV trucks, which might limit interest in adopting improved internal combustion engines. However, hydrogen-powered trucks face the formidable challenges of producing zero GHG hydrogen at affordable cost, as well as the cost of storage and transportation of hydrogen. At present the high purity hydrogen needed for fuel cells is generally very expensive.

      Q. How does your idea compare overall to battery-powered and hydrogen-powered HDVs? And how will you persuade people that it is an attractive pathway to follow?

      A. Our design uses existing propulsion systems and can operate on existing liquid fuels, and for these reasons, in the near term, it will be economically attractive to the operators of long-haul trucks. In fact, it can even be a lower-cost option than diesel power because of the significantly less-expensive exhaust treatment and smaller-size engines for the same power and torque. This economic attractiveness could enable the large-scale market penetration that is needed to have a substantial impact on reducing air pollution. Alternatively, we think it could take at least 20 years longer for BEVs or hydrogen-powered vehicles to obtain the same level of market penetration.

      Our approach also uses existing corn-based ethanol, which can provide a greater near-term GHG reduction benefit than battery- or hydrogen-powered long-haul trucks. While the GHG reduction from using existing ethanol would initially be in the 20 percent to 40 percent range, the scale at which the market is penetrated in the near-term could be much greater than for BEV or hydrogen-powered vehicle technology. The overall impact in reducing GHGs could be considerably greater.

      Moreover, we see a migration path beyond 2030 where further reductions in GHG emissions from corn ethanol can be possible through carbon capture and sequestration of the carbon dioxide (CO2) that is produced during ethanol production. In this case, overall CO2 reductions could potentially be 80 percent or more. Technologies for producing ethanol (and methanol, another alcohol fuel) from waste at attractive costs are emerging, and can provide fuel with zero or negative GHG emissions. One pathway for providing a negative GHG impact is through finding alternatives to landfilling for waste disposal, as this method leads to potent methane GHG emissions. A negative GHG impact could also be obtained by converting biomass waste into clean fuel, since the biomass waste can be carbon neutral and CO2 from the production of the clean fuel can be captured and sequestered.

      In addition, our flex-fuel engine technology may be synergistically used as range extenders in plug-in hybrid HDVs, which use limited battery capacity and obviates the cargo capability reduction and fueling disadvantages of long-haul trucks powered by battery alone.

      With the growing threats from air pollution and global warming, our HDV solution is an increasingly important option for near-term reduction of air pollution and offers a faster start in reducing heavy-duty fleet GHG emissions. It also provides an attractive migration path for longer-term, larger GHG reductions from the HDV sector. More

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      in Environment

      Smarter regulation of global shipping emissions could improve air quality and health outcomes

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      Emissions from shipping activities around the world account for nearly 3 percent of total human-caused greenhouse gas emissions, and could increase by up to 50 percent by 2050, making them an important and often overlooked target for global climate mitigation. At the same time, shipping-related emissions of additional pollutants, particularly nitrogen and sulfur oxides, pose a significant threat to global health, as they degrade air quality enough to cause premature deaths.

      The main source of shipping emissions is the combustion of heavy fuel oil in large diesel engines, which disperses pollutants into the air over coastal areas. The nitrogen and sulfur oxides emitted from these engines contribute to the formation of PM2.5, airborne particulates with diameters of up to 2.5 micrometers that are linked to respiratory and cardiovascular diseases. Previous studies have estimated that PM2.5  from shipping emissions contribute to about 60,000 cardiopulmonary and lung cancer deaths each year, and that IMO 2020, an international policy that caps engine fuel sulfur content at 0.5 percent, could reduce PM2.5 concentrations enough to lower annual premature mortality by 34 percent.

      Global shipping emissions arise from both domestic (between ports in the same country) and international (between ports of different countries) shipping activities, and are governed by national and international policies, respectively. Consequently, effective mitigation of the air quality and health impacts of global shipping emissions will require that policymakers quantify the relative contributions of domestic and international shipping activities to these adverse impacts in an integrated global analysis.

      A new study in the journal Environmental Research Letters provides that kind of analysis for the first time. To that end, the study’s co-authors — researchers from MIT and the Hong Kong University of Science and Technology — implement a three-step process. First, they create global shipping emission inventories for domestic and international vessels based on ship activity records of the year 2015 from the Automatic Identification System (AIS). Second, they apply an atmospheric chemistry and transport model to this data to calculate PM2.5 concentrations generated by that year’s domestic and international shipping activities. Finally, they apply a model that estimates mortalities attributable to these pollutant concentrations.

      The researchers find that approximately 94,000 premature deaths were associated with PM2.5 exposure due to maritime shipping in 2015 — 83 percent international and 17 percent domestic. While international shipping accounted for the vast majority of the global health impact, some regions experienced significant health burdens from domestic shipping operations. This is especially true in East Asia: In China, 44 percent of shipping-related premature deaths were attributable to domestic shipping activities.

      “By comparing the health impacts from international and domestic shipping at the global level, our study could help inform decision-makers’ efforts to coordinate shipping emissions policies across multiple scales, and thereby reduce the air quality and health impacts of these emissions more effectively,” says Yiqi Zhang, a researcher at the Hong Kong University of Science and Technology who led the study as a visiting student supported by the MIT Joint Program on the Science and Policy of Global Change.

      In addition to estimating the air-quality and health impacts of domestic and international shipping, the researchers evaluate potential health outcomes under different shipping emissions-control policies that are either currently in effect or likely to be implemented in different regions in the near future.

      They estimate about 30,000 avoided deaths per year under a scenario consistent with IMO 2020, an international regulation limiting the sulfur content in shipping fuel oil to 0.5 percent — a finding that tracks with previous studies. Further strengthening regulations on sulfur content would yield only slight improvement; limiting sulfur content to 0.1 percent reduces annual shipping-attributable PM2.5-related premature deaths by an additional 5,000. In contrast, regulating nitrogen oxides instead, involving a Tier III NOx Standard would produce far greater benefits than a 0.1-percent sulfur cap, with 33,000 further avoided deaths.

      “Areas with high proportions of mortalities contributed by domestic shipping could effectively use domestic regulations to implement controls,” says study co-author Noelle Selin, a professor at MIT’s Institute for Data, Systems and Society and Department of Earth, Atmospheric and Planetary Sciences, and a faculty affiliate of the MIT Joint Program. “For other regions where much damage comes from international vessels, further international cooperation is required to mitigate impacts.” More

    • 188 Shares169 Views

      in Energy

      Using aluminum and water to make clean hydrogen fuel — when and where it’s needed

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      As the world works to move away from fossil fuels, many researchers are investigating whether clean hydrogen fuel can play an expanded role in sectors from transportation and industry to buildings and power generation. It could be used in fuel cell vehicles, heat-producing boilers, electricity-generating gas turbines, systems for storing renewable energy, and more.

      But while using hydrogen doesn’t generate carbon emissions, making it typically does. Today, almost all hydrogen is produced using fossil fuel-based processes that together generate more than 2 percent of all global greenhouse gas emissions. In addition, hydrogen is often produced in one location and consumed in another, which means its use also presents logistical challenges.

      A promising reaction

      Another option for producing hydrogen comes from a perhaps surprising source: reacting aluminum with water. Aluminum metal will readily react with water at room temperature to form aluminum hydroxide and hydrogen. That reaction doesn’t typically take place because a layer of aluminum oxide naturally coats the raw metal, preventing it from coming directly into contact with water.

      Using the aluminum-water reaction to generate hydrogen doesn’t produce any greenhouse gas emissions, and it promises to solve the transportation problem for any location with available water. Simply move the aluminum and then react it with water on-site. “Fundamentally, the aluminum becomes a mechanism for storing hydrogen — and a very effective one,” says Douglas P. Hart, professor of mechanical engineering at MIT. “Using aluminum as our source, we can ‘store’ hydrogen at a density that’s 10 times greater than if we just store it as a compressed gas.”

      Two problems have kept aluminum from being employed as a safe, economical source for hydrogen generation. The first problem is ensuring that the aluminum surface is clean and available to react with water. To that end, a practical system must include a means of first modifying the oxide layer and then keeping it from re-forming as the reaction proceeds.

      The second problem is that pure aluminum is energy-intensive to mine and produce, so any practical approach needs to use scrap aluminum from various sources. But scrap aluminum is not an easy starting material. It typically occurs in an alloyed form, meaning that it contains other elements that are added to change the properties or characteristics of the aluminum for different uses. For example, adding magnesium increases strength and corrosion-resistance, adding silicon lowers the melting point, and adding a little of both makes an alloy that’s moderately strong and corrosion-resistant.

      Despite considerable research on aluminum as a source of hydrogen, two key questions remain: What’s the best way to prevent the adherence of an oxide layer on the aluminum surface, and how do alloying elements in a piece of scrap aluminum affect the total amount of hydrogen generated and the rate at which it is generated?

      “If we’re going to use scrap aluminum for hydrogen generation in a practical application, we need to be able to better predict what hydrogen generation characteristics we’re going to observe from the aluminum-water reaction,” says Laureen Meroueh PhD ’20, who earned her doctorate in mechanical engineering.

      Since the fundamental steps in the reaction aren’t well understood, it’s been hard to predict the rate and volume at which hydrogen forms from scrap aluminum, which can contain varying types and concentrations of alloying elements. So Hart, Meroueh, and Thomas W. Eagar, a professor of materials engineering and engineering management in the MIT Department of Materials Science and Engineering, decided to examine — in a systematic fashion — the impacts of those alloying elements on the aluminum-water reaction and on a promising technique for preventing the formation of the interfering oxide layer.

      To prepare, they had experts at Novelis Inc. fabricate samples of pure aluminum and of specific aluminum alloys made of commercially pure aluminum combined with either 0.6 percent silicon (by weight), 1 percent magnesium, or both — compositions that are typical of scrap aluminum from a variety of sources. Using those samples, the MIT researchers performed a series of tests to explore different aspects of the aluminum-water reaction.

      Pre-treating the aluminum

      The first step was to demonstrate an effective means of penetrating the oxide layer that forms on aluminum in the air. Solid aluminum is made up of tiny grains that are packed together with occasional boundaries where they don’t line up perfectly. To maximize hydrogen production, researchers would need to prevent the formation of the oxide layer on all those interior grain surfaces.

      Research groups have already tried various ways of keeping the aluminum grains “activated” for reaction with water. Some have crushed scrap samples into particles so tiny that the oxide layer doesn’t adhere. But aluminum powders are dangerous, as they can react with humidity and explode. Another approach calls for grinding up scrap samples and adding liquid metals to prevent oxide deposition. But grinding is a costly and energy-intensive process.

      To Hart, Meroueh, and Eagar, the most promising approach — first introduced by Jonathan Slocum ScD ’18 while he was working in Hart’s research group — involved pre-treating the solid aluminum by painting liquid metals on top and allowing them to permeate through the grain boundaries.

      To determine the effectiveness of that approach, the researchers needed to confirm that the liquid metals would reach the internal grain surfaces, with and without alloying elements present. And they had to establish how long it would take for the liquid metal to coat all of the grains in pure aluminum and its alloys.

      They started by combining two metals — gallium and indium — in specific proportions to create a “eutectic” mixture; that is, a mixture that would remain in liquid form at room temperature. They coated their samples with the eutectic and allowed it to penetrate for time periods ranging from 48 to 96 hours. They then exposed the samples to water and monitored the hydrogen yield (the amount formed) and flow rate for 250 minutes. After 48 hours, they also took high-magnification scanning electron microscope (SEM) images so they could observe the boundaries between adjacent aluminum grains.

      Based on the hydrogen yield measurements and the SEM images, the MIT team concluded that the gallium-indium eutectic does naturally permeate and reach the interior grain surfaces. However, the rate and extent of penetration vary with the alloy. The permeation rate was the same in silicon-doped aluminum samples as in pure aluminum samples but slower in magnesium-doped samples.

      Perhaps most interesting were the results from samples doped with both silicon and magnesium — an aluminum alloy often found in recycling streams. Silicon and magnesium chemically bond to form magnesium silicide, which occurs as solid deposits on the internal grain surfaces. Meroueh hypothesized that when both silicon and magnesium are present in scrap aluminum, those deposits can act as barriers that impede the flow of the gallium-indium eutectic.

      The experiments and images confirmed her hypothesis: The solid deposits did act as barriers, and images of samples pre-treated for 48 hours showed that permeation wasn’t complete. Clearly, a lengthy pre-treatment period would be critical for maximizing the hydrogen yield from scraps of aluminum containing both silicon and magnesium.

      Meroueh cites several benefits to the process they used. “You don’t have to apply any energy for the gallium-indium eutectic to work its magic on aluminum and get rid of that oxide layer,” she says. “Once you’ve activated your aluminum, you can drop it in water, and it’ll generate hydrogen — no energy input required.” Even better, the eutectic doesn’t chemically react with the aluminum. “It just physically moves around in between the grains,” she says. “At the end of the process, I could recover all of the gallium and indium I put in and use it again” — a valuable feature as gallium and (especially) indium are costly and in relatively short supply.

      Impacts of alloying elements on hydrogen generation

      The researchers next investigated how the presence of alloying elements affects hydrogen generation. They tested samples that had been treated with the eutectic for 96 hours; by then, the hydrogen yield and flow rates had leveled off in all the samples.

      The presence of 0.6 percent silicon increased the hydrogen yield for a given weight of aluminum by 20 percent compared to pure aluminum — even though the silicon-containing sample had less aluminum than the pure aluminum sample. In contrast, the presence of 1 percent magnesium produced far less hydrogen, while adding both silicon and magnesium pushed the yield up, but not to the level of pure aluminum.

      The presence of silicon also greatly accelerated the reaction rate, producing a far higher peak in the flow rate but cutting short the duration of hydrogen output. The presence of magnesium produced a lower flow rate but allowed the hydrogen output to remain fairly steady over time. And once again, aluminum with both alloying elements produced a flow rate between that of magnesium-doped and pure aluminum.

      Those results provide practical guidance on how to adjust the hydrogen output to match the operating needs of a hydrogen-consuming device. If the starting material is commercially pure aluminum, adding small amounts of carefully selected alloying elements can tailor the hydrogen yield and flow rate. If the starting material is scrap aluminum, careful choice of the source can be key. For high, brief bursts of hydrogen, pieces of silicon-containing aluminum from an auto junkyard could work well. For lower but longer flows, magnesium-containing scraps from the frame of a demolished building might be better. For results somewhere in between, aluminum containing both silicon and magnesium should work well; such material is abundantly available from scrapped cars and motorcycles, yachts, bicycle frames, and even smartphone cases.

      It should also be possible to combine scraps of different aluminum alloys to tune the outcome, notes Meroueh. “If I have a sample of activated aluminum that contains just silicon and another sample that contains just magnesium, I can put them both into a container of water and let them react,” she says. “So I get the fast ramp-up in hydrogen production from the silicon and then the magnesium takes over and has that steady output.”

      Another opportunity for tuning: Reducing grain size

      Another practical way to affect hydrogen production could be to reduce the size of the aluminum grains — a change that should increase the total surface area available for reactions to occur.

      To investigate that approach, the researchers requested specially customized samples from their supplier. Using standard industrial procedures, the Novelis experts first fed each sample through two rollers, squeezing it from the top and bottom so that the internal grains were flattened. They then heated each sample until the long, flat grains had reorganized and shrunk to a targeted size.

      In a series of carefully designed experiments, the MIT team found that reducing the grain size increased the efficiency and decreased the duration of the reaction to varying degrees in the different samples. Again, the presence of particular alloying elements had a major effect on the outcome.

      Needed: A revised theory that explains observations

      Throughout their experiments, the researchers encountered some unexpected results. For example, standard corrosion theory predicts that pure aluminum will generate more hydrogen than silicon-doped aluminum will — the opposite of what they observed in their experiments.

      To shed light on the underlying chemical reactions, Hart, Meroueh, and Eagar investigated hydrogen “flux,” that is, the volume of hydrogen generated over time on each square centimeter of aluminum surface, including the interior grains. They examined three grain sizes for each of their four compositions and collected thousands of data points measuring hydrogen flux.

      Their results show that reducing grain size has significant effects. It increases the peak hydrogen flux from silicon-doped aluminum as much as 100 times and from the other three compositions by 10 times. With both pure aluminum and silicon-containing aluminum, reducing grain size also decreases the delay before the peak flux and increases the rate of decline afterward. With magnesium-containing aluminum, reducing the grain size brings about an increase in peak hydrogen flux and results in a slightly faster decline in the rate of hydrogen output. With both silicon and magnesium present, the hydrogen flux over time resembles that of magnesium-containing aluminum when the grain size is not manipulated. When the grain size is reduced, the hydrogen output characteristics begin to resemble behavior observed in silicon-containing aluminum. That outcome was unexpected because when silicon and magnesium are both present, they react to form magnesium silicide, resulting in a new type of aluminum alloy with its own properties.

      The researchers stress the benefits of developing a better fundamental understanding of the underlying chemical reactions involved. In addition to guiding the design of practical systems, it might help them find a replacement for the expensive indium in their pre-treatment mixture. Other work has shown that gallium will naturally permeate through the grain boundaries of aluminum. “At this point, we know that the indium in our eutectic is important, but we don’t really understand what it does, so we don’t know how to replace it,” says Hart.

      But already Hart, Meroueh, and Eagar have demonstrated two practical ways of tuning the hydrogen reaction rate: by adding certain elements to the aluminum and by manipulating the size of the interior aluminum grains. In combination, those approaches can deliver significant results. “If you go from magnesium-containing aluminum with the largest grain size to silicon-containing aluminum with the smallest grain size, you get a hydrogen reaction rate that differs by two orders of magnitude,” says Meroueh. “That’s huge if you’re trying to design a real system that would use this reaction.”

      This research was supported through the MIT Energy Initiative by ExxonMobil-MIT Energy Fellowships awarded to Laureen Meroueh PhD ’20 from 2018 to 2020.

      This article appears in the Spring 2021 issue of Energy Futures, the magazine of the MIT Energy Initiative.  More

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      in Environment

      Using graphene foam to filter toxins from drinking water

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

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

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

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

      Targeting the contaminant

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

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

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

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

      Simple, efficient, and clean

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

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

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

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

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

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

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

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      in Energy

      A material difference

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

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

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

      A material world

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

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

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

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

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

      Enthusiasm for innovation

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

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

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

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

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

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

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

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

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      in Energy

      Reducing emissions by decarbonizing industry

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

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

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

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

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

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

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

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

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

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

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