A recipe for zero-emissions fuel: Soda cans, seawater, and caffeine

A sustainable source for clean energy may lie in old soda cans and seawater.

MIT engineers have found that when the aluminum in soda cans is exposed in its pure form and mixed with seawater, the solution bubbles up and naturally produces hydrogen -- a gas that can be subsequently used to power an engine or fuel cell without generating carbon emissions. What's more, this simple reaction can be sped up by adding a common stimulant: caffeine.

In a study appearing today in the journal Cell Reports Physical Science, the researchers show they can produce hydrogen gas by dropping pretreated, pebble-sized aluminum pellets into a beaker of filtered seawater. The aluminum is pretreated with a rare-metal alloy that effectively scrubs aluminum into a pure form that can react with seawater to generate hydrogen. The salt ions in the seawater can in turn attract and recover the alloy, which can be reused to generate more hydrogen, in a sustainable cycle.

The team found that this reaction between aluminum and seawater successfully produces hydrogen gas, though slowly. On a lark, they tossed into the mix some coffee grounds and found, to their surprise, that the reaction picked up its pace.

In the end, the team discovered that a low concentration of imidazole -- an active ingredient in caffeine -- is enough to significantly speed up the reaction, producing the same amount of hydrogen in just five minutes, compared to two hours without the added stimulant.

The researchers are developing a small reactor that could run on a marine vessel or underwater vehicle. The vessel would hold a supply of aluminum pellets (recycled from old soda cans and other aluminum products), along with a small amount of gallium-indium and caffeine. These ingredients could be periodically funneled into the reactor, along with some of the surrounding seawater, to produce hydrogen on demand. The hydrogen could then fuel an onboard engine to drive a motor or generate electricity to power the ship.

"This is very interesting for maritime applications like boats or underwater vehicles because you wouldn't have to carry around seawater -- it's readily available," says study lead author Aly Kombargi, a PhD student in MIT's Department of Mechanical Engineering. "We also don't have to carry a tank of hydrogen. Instead, we would transport aluminum as the 'fuel,' and just add water to produce the hydrogen that we need."

The study's co-authors include Enoch Ellis, an undergraduate in chemical engineering; Peter Godart PhD '21, who has founded a company to recycle aluminum as a source of hydrogen fuel; and Douglas Hart, MIT professor of mechanical engineering.

Shields up

The MIT team, led by Hart, is developing efficient and sustainable methods to produce hydrogen gas, which is seen as a "green" energy source that could power engines and fuel cells without generating climate-warming emissions.

One drawback to fueling vehicles with hydrogen is that some designs would require the gas to be carried onboard like traditional gasoline in a tank -- a risky setup, given hydrogen's volatile potential. Hart and his team have instead looked for ways to power vehicles with hydrogen without having to constantly transport the gas itself.

They found a possible workaround in aluminum -- a naturally abundant and stable material that, when in contact with water, undergoes a straightforward chemical reaction that generates hydrogen and heat.

The reaction, however, comes with a sort of Catch-22: While aluminum can generate hydrogen when it mixes with water, it can only do so in a pure, exposed state. The instant aluminum meets with oxygen, such as in air, the surface immediately forms a thin, shield-like layer of oxide that prevents further reactions. This barrier is the reason hydrogen doesn't immediately bubble up when you drop a soda can in water.

In previous work, using fresh water, the team found they could pierce aluminum's shield and keep the reaction with water going by pretreating the aluminum with a small amount of rare metal alloy made from a specific concentration of gallium and indium. The alloy serves as an "activator," scrubbing away any oxide buildup and creating a pure aluminum surface that is free to react with water. When they ran the reaction in fresh, de-ionized water, they found that one pretreated pellet of aluminum produced 400 milliliters of hydrogen in just five minutes. They estimate that just 1 gram of pellets would generate 1.3 liters of hydrogen in the same amount of time.

But to further scale up the system would require a significant supply of gallium indium, which is relatively expensive and rare.

"For this idea to be cost-effective and sustainable, we had to work on recovering this alloy postreaction," Kombargi says.

By the sea

In the team's new work, they found they could retrieve and reuse gallium indium using a solution of ions. The ions -- atoms or molecules with an electrical charge -- protect the metal alloy from reacting with water and help it to precipitate into a form that can be scooped out and reused.

"Lucky for us, seawater is an ionic solution that is very cheap and available," says Kombargi, who tested the idea with seawater from a nearby beach. "I literally went to Revere Beach with a friend and we grabbed our bottles and filled them, and then I just filtered out algae and sand, added aluminum to it, and it worked with the same consistent results."

He found that hydrogen indeed bubbled up when he added aluminum to a beaker of filtered seawater. And he was able to scoop out the gallium indium afterward. But the reaction happened much more slowly than it did in fresh water. It turns out that the ions in seawater act to shield gallium indium, such that it can coalesce and be recovered after the reaction. But the ions have a similar effect on aluminum, building up a barrier that slows its reaction with water.

As they looked for ways to speed up the reaction in seawater, the researchers tried out various and unconventional ingredients.

"We were just playing around with things in the kitchen, and found that when we added coffee grounds into seawater and dropped aluminum pellets in, the reaction was quite fast compared to just seawater," Kombargi says.

To see what might explain the speedup, the team reached out to colleagues in MIT's chemistry department, who suggested they try imidazole -- an active ingredient in caffeine, which happens to have a molecular structure that can pierce through aluminum (allowing the material to continue reacting with water), while leaving gallium indium's ionic shield intact.

"That was our big win," Kombargi says. "We had everything we wanted: recovering the gallium indium, plus the fast and efficient reaction."

The researchers believe they have the essential ingredients to run a sustainable hydrogen reactor. They plan to test it first in marine and underwater vehicles. They've calculated that such a reactor, holding about 40 pounds of aluminum pellets, could power a small underwater glider for about 30 days by pumping in surrounding seawater and generating hydrogen to power a motor.

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Generating power with blood sugar

In type 1 diabetes, the body does not produce insulin. This means that patients have to obtain the hormone externally to regulate their blood sugar levels. Nowadays, this is mostly done via insulin pumps that are attached directly to the body. These devices, as well as other medical applications such as pacemakers, require a reliable energy supply, which at present is met primarily by power from either single-use or rechargeable batteries.

Now, a team of researchers led by Martin Fussenegger from the Department of Biosystems Science and Engineering at ETH Zurich in Basel have put a seemingly futuristic idea into practice. They have developed an implantable fuel cell that uses excess blood sugar (glucose) from tissue to generate electrical energy. The researchers have combined the fuel cell with artificial beta cells developed by their group several years ago. These produce insulin at the touch of a button and effectively lower blood glucose levels much like their natural role models in the pancreas.

"Many people, especially in the Western industrialised nations, consume more carbohydrates than they need in everyday life," Fussenegger explains. This, he adds, leads to obesity, diabetes and cardiovascular disease. "This gave us the idea of using this excess metabolic energy to produce electricity to power biomedical devices," he says.

Fuel cell in tea bag format

At the heart of the fuel cell is an anode (electrode) made of copper-based nanoparticles, which Fussenegger's team created specifically for this application. It consists of copper-based nanoparticles and splits glucose into gluconic acid and a proton to generate electricity, which sets an electric circuit in motion.

Wrapped in a nonwoven fabric and coated with alginate, an algae product approved for medical use, the fuel cell resembles a small tea bag that can be implanted under the skin. The alginate soaks up body fluid and allows glucose to pass from the tissue into the fuel cell within.

A diabetes network with its own power supply

In a second step, the researchers coupled the fuel cell with a capsule containing artificial beta cells. These can be stimulated to produce and secrete insulin using electric current or blue LED light. Fussenegger and his colleagues already tested such designer cells some time ago (see ETH News, 8 December 2016).

The system combines sustained power generation and controlled insulin delivery. As soon as the fuel cell registers excess glucose, it starts to generate power. This electrical energy is then used to stimulate the cells to produce and release insulin into the blood. As a result, blood sugar dips to a normal level. Once it falls below a certain threshold value, the production of electricity and insulin stops.

The electrical energy provided by the fuel cell is sufficient not only to stimulate the designer cells but also to enable the implanted system to communicate with external devices such as a smartphone. This allows potential users to adjust the system via a corresponding app. A doctor could also access it remotely and make adjustments. "The new system autonomously regulates insulin and blood glucose levels and could be used to treat diabetes in the future," Fussenegger says.

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Extract from a common kitchen spice could be key to greener, more efficient fuel cells

Turmeric, a spice found in most kitchens, has an extract that could lead to safer, more efficient fuel cells.

Researchers at the Clemson Nanomaterials Institute (CNI) and their collaborators from the Sri Sathya Sai Institute of Higher Learning (SSSIHL) in India discovered a novel way to combine curcumin -- the substance in turmeric -- and gold nanoparticles to create an electrode that requires 100 times less energy to efficiently convert ethanol into electricity.

While the research team must do more testing, the discovery brings replacing hydrogen as a fuel cell feedstock one step closer.

"Of all the catalysts for alcohol oxidation in alkaline medium, the one we prepared is the best so far," said Apparao Rao, CNI's founding director and the R. A. Bowen Professor of Physics in the College of Science's.

Fuel cells generate electricity through a chemical reaction instead of combustion. They are used to power vehicles, buildings, portable electronic devices and backup power systems.

Hydrogen fuel cells are highly efficient and do not produce greenhouse gases. While hydrogen is the most common chemical element in the universe, it must be derived from substances such as natural gas and fossil fuels because it occurs naturally on Earth only in compound form with other elements in liquids, gases or solids. The necessary extraction adds to hydrogen fuel cells' cost and environmental impact.

In addition, hydrogen used in fuel cells is a compressed gas, creating challenges for storage and transportation. Ethanol, an alcohol made from corn or other agricultural-based feeds, is safer and easier to transport than hydrogen because it is a liquid.

"To make it a commercial product where we can fill our tanks with ethanol, the electrodes have to be highly efficient," said Lakshman Ventrapragada, a former student of Rao's who worked as a research assistant at the CNI and is an alumnus of SSSIHL. "At the same time, we don't want very expensive electrodes or synthetic polymeric substrates that are not eco-friendly because that defeats the whole purpose. We wanted to look at something green for the fuel cell generation process and making the fuel cell itself."

The researchers focused on the fuel cell's anode, where the ethanol or other feed source is oxidized.

Fuel cells widely use platinum as a catalyst. But platinum suffers from poisoning because of reaction intermediates such as carbon monoxide, Ventrapragada said. It is also costly.

The researchers used gold as a catalyst. Instead of using conducting polymers, metal-organic frameworks, or other complex materials to deposit the gold on the surface of the electrode, the researchers used curcumin because of its structural uniqueness. Curcumin is used to decorate the gold nanoparticles to stabilize them, forming a porous network around the nanoparticles. Researchers deposited the curcumin gold nanoparticle on the surface of the electrode at a 100 times lower electric current than in previous studies.

Without the curcumin coating, the gold nanoparticles agglomerate, cutting down on the surface area exposed to the chemical reaction, Ventrapragada said.

"Without this curcumin coating, the performance is poor," Rao said. "We need this coating to stabilize and create a porous environment around the nanoparticles, and then they do a super job with alcohol oxidation.

"There's a big push in the industry for alcohol oxidation. This discovery is an excellent enabler for that. The next step is to scale the process up and work with an industrial collaborator who can actually make the fuel cells and build stacks of fuel cells for the real application," he continued.

But the research could have broader implications than improved fuel cells. The electrode's unique properties could lend itself to future applications in sensors, supercapacitors and more, Ventrapragada said.

In collaboration with the SSSIHL research team, Rao's team is testing the electrode as a sensor that could help identify changes in the level of dopamine. Dopamine has been implicated in disorders such as Parkinson's disease and attention deficit hyperactivity disorder. When members of the research team tested urine samples obtained from healthy volunteers, they could measure dopamine to the approved clinical range with this electrode using a cost-effective method compared to standard ones used today, Rao said.

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Researchers develop tool to aid in development, efficiency of hydrogen-powered cars

Widespread adoption of hydrogen-powered vehicles over traditional electric vehicles requires fuel cells that can convert hydrogen and oxygen safely into water -- a serious implementation problem.

Researchers at the University of Colorado Boulder are addressing one aspect of that roadblock by developing new computational tools and models needed to better understand and manage the conversion process. Hendrik Heinz, an associate professor in the Department of Chemical and Biological Engineering, is leading the effort in partnership with the University of California Los Angeles. His team recently published new findings on the subject in Science Advances.

Fuel cell electric vehicles combine hydrogen in a tank with oxygen taken from the air to produce the electricity needed to run. They don't need to be plugged in to charge and have the added benefit of producing water vapor as a byproduct. Those, plus other factors, have made them an intriguing option in the green and renewable energy transportation areas.

Heinz said a key goal to making the vehicles viable is to find an effective catalyst in the fuel cell that can "burn" the hydrogen with oxygen under controlled conditions needed for safe travel. At the same time, researchers are looking for a catalyst that can do this at near room temperature, with high efficiency and a long lifetime in acidic solution. Platinum metal is commonly used, but predicting the reactions and best materials to use for scaling up or different conditions has been a challenge to date.

"For decades, researchers have struggled to predict the complex processes needed for this work, though enormous progress has been made using nanoplates, nanowires and many other nanostructures," Heinz said. "To address this, we have developed models for metal nanostructures and oxygen, water and metal interactions that exceed the accuracy of current quantum methods by more than 10 times. The models also enable the inclusion of the solvent and dynamics and reveal quantitative correlations between oxygen accessibility to the surface and catalytic activity in the oxygen reduction reaction."

Heinz said the quantitative simulations his team developed show the interaction between oxygen molecules as they encounter different barriers by molecular layers of water on the platinum surface. These interactions make the difference between a slow or fast follow-on reaction and need to be controlled for the process to work efficiently. These reactions happen quite fast -- the conversion into water takes about a millisecond per square nanometer to complete -- and happen on a tiny catalyst surface. All of those variables come together in an intricate, complex "dance" that his team has found a way to model in predictive ways.

The computational and data-intensive methods described in the paper can be used to create designer-nanostructures that would max out the catalytic efficiency, as well as possible surface modifications to further optimize the cost-benefit ratio of fuel cells, Heinz added. His collaborators are exploring the commercial implication of that aspect, and he is applying the tools to help to study a wider range of potential alloys and gain further insights into the mechanics at play.

"The tools described in the paper, especially the interface force field for order-of-magnitude more reliable molecular dynamics simulations, can also be applied to other catalyst and electrocatalyst interfaces for similar groundbreaking and practically useful advances," he said.

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