Tag Archives: fuel cells

Everlasting dirt-powered sensors for agriculture?

Caption: The fuel cell’s 3D printed cap peeks above the ground. The cap keeps debris out of the device while enabling air flow. Credit: Bill Yen/Northwestern University

A January 12, 2024 Northwestern University news release (also received via email and also on EurekAlert both published January 15, 2024) describes this dirt-powered research from the US, Note: Links have been removed,

*New fuel cell harnesses naturally occurring microbes to generate electricity

*Soil-powered sensors to successfully monitor soil moisture and detect touch

*New tech was robust enough to withstand drier soil conditions and flooding

*Fuel cell could replace batteries in sensors used for precision agriculture

EVANSTON, Ill. — A Northwestern University-led team of researchers has developed a new fuel cell that harvests energy from microbes living in dirt. 

About the size of a standard paperback book, the completely soil-powered technology could fuel underground sensors used in precision agriculture and green infrastructure. This potentially could offer a sustainable, renewable alternative to batteries, which hold toxic, flammable chemicals that leach into the ground, are fraught with conflict-filled supply chains and contribute to the ever-growing problem of electronic waste.

To test the new fuel cell, the researchers used it to power sensors measuring soil moisture and detecting touch, a capability that could be valuable for tracking passing animals. To enable wireless communications, the researchers also equipped the soil-powered sensor with a tiny antenna to transmit data to a neighboring base station by reflecting existing radio frequency signals.

Not only did the fuel cell work in both wet and dry conditions, but its power also outlasted similar technologies by 120%.

The research will be published today (Jan. 12 [2024]) in the Proceedings of the Association for Computing Machinery on Interactive, Mobile, Wearable and Ubiquitous Technologies. The study authors also are releasing all designs, tutorials and simulation tools to the public, so others may use and build upon the research.

“The number of devices in the Internet of Things (IoT) is constantly growing,” said Northwestern alumnus Bill Yen, who led the work. “If we imagine a future with trillions of these devices, we cannot build every one of them out of lithium, heavy metals and toxins that are dangerous to the environment. We need to find alternatives that can provide low amounts of energy to power a decentralized network of devices. In a search for solutions, we looked to soil microbial fuel cells, which use special microbes to break down soil and use that low amount of energy to power sensors. As long as there is organic carbon in the soil for the microbes to break down, the fuel cell can potentially last forever.”

“These microbes are ubiquitous; they already live in soil everywhere,” said Northwestern’s George Wells, a senior author on the study. “We can use very simple engineered systems to capture their electricity. We’re not going to power entire cities with this energy. But we can capture minute amounts of energy to fuel practical, low-power applications.”

Wells is an associate professor of civil and environmental engineering at Northwestern’s McCormick School of Engineering. Now a Ph.D. student at Stanford University, Yen started this project when he was an undergraduate researcher in Wells’ laboratory.

Solutions for a dirty job

In recent years, farmers worldwide increasingly have adopted precision agriculture as a strategy to improve crop yields. The tech-driven approach relies on measuring precise levels of moisture, nutrients and contaminants in soil to make decisions that enhance crop health. This requires a widespread, dispersed network of electronic devices to continuously collect environmental data.

“If you want to put a sensor out in the wild, in a farm or in a wetland, you are constrained to putting a battery in it or harvesting solar energy,” Yen said. “Solar panels don’t work well in dirty environments because they get covered with dirt, do not work when the sun isn’t out and take up a lot of space. Batteries also are challenging because they run out of power. Farmers are not going to go around a 100-acre farm to regularly swap out batteries or dust off solar panels.”

To overcome these challenges, Wells, Yen and their collaborators wondered if they could instead harvest energy from the existing environment. “We could harvest energy from the soil that farmers are monitoring anyway,” Yen said.

‘Stymied efforts’

Making their first appearance in 1911, soil-based microbial fuel cells (MFCs) operate like a battery — with an anode, cathode and electrolyte. But instead of using chemicals to generate electricity, MFCs harvest electricity from bacteria that naturally donate electrons to nearby conductors. When these electrons flow from the anode to the cathode, it creates an electric circuit.

But in order for microbial fuel cells to operate without disruption, they need to stay hydrated and oxygenated — which is tricky when buried underground within dry dirt.

“Although MFCs have existed as a concept for more than a century, their unreliable performance and low output power have stymied efforts to make practical use of them, especially in low-moisture conditions,” Yen said.

Winning geometry

With these challenges in mind, Yen and his team embarked on a two-year journey to develop a practical, reliable soil-based MFC. His expedition included creating — and comparing — four different versions. First, the researchers collected a combined nine months of data on the performance of each design. Then, they tested their final version in an outdoor garden.

The best-performing prototype worked well in dry conditions as well as within a water-logged environment. The secret behind its success: Its geometry. Instead of using a traditional design, in which the anode and cathode are parallel to one another, the winning fuel cell leveraged a perpendicular design.

Made of carbon felt (an inexpensive, abundant conductor to capture the microbes’ electrons), the anode is horizontal to the ground’s surface. Made of an inert, conductive metal, the cathode sits vertically atop the anode. 

Although the entire device is buried, the vertical design ensures that the top end is flush with the ground’s surface. A 3D-printed cap rests on top of the device to prevent debris from falling inside. And a hole on top and an empty air chamber running alongside the cathode enable consistent airflow.  

The lower end of the cathode remains nestled deep beneath the surface, ensuring that it stays hydrated from the moist, surrounding soil — even when the surface soil dries out in the sunlight. The researchers also coated part of the cathode with waterproofing material to allow it to breathe during a flood. And, after a potential flood, the vertical design enables the cathode to dry out gradually rather than all at once.

On average, the resulting fuel cell generated 68 times more power than needed to operate its sensors. It also was robust enough to withstand large changes in soil moisture — from somewhat dry (41% water by volume) to completely underwater.

Making computing accessible

The researchers say all components for their soil-based MFC can be purchased at a local hardware store. Next, they plan to develop a soil-based MFC made from fully biodegradable materials. Both designs bypass complicated supply chains and avoid using conflict minerals.

“With the COVID-19 pandemic, we all became familiar with how a crisis can disrupt the global supply chain for electronics,” said study co-author Josiah Hester, a former Northwestern faculty member who is now at the Georgia Institute of Technology. “We want to build devices that use local supply chains and low-cost materials so that computing is accessible for all communities.”

The study, “Soil-powered computing: The engineer’s guide to practical soil microbial fuel cell design,” was supported by the National Science Foundation (award number CNS-2038853), the Agricultural and Food Research Initiative (award number 2023-67021-40628) from the USDA National Institute of Food and Agriculture, the Alfred P. Sloan Foundation, VMware Research and 3M.

Here’s a link to and a citation for the paper,

Soil-Powered Computing: The Engineer’s Guide to Practical Soil Microbial Fuel Cell Design by Bill Yen, Laura Jaliff, Louis Gutierrez, Philothei Sahinidis, Sadie Bernstein, John Madden, Stephen Taylor, Colleen Josephson, Pat Pannuto, Weitao Shuai, George Wells, Nivedita Arora, Josiah Hester. Proceedings of the ACM on Interactive, Mobile, Wearable and Ubiquitous Technologies Volume 7 Issue 4 Article No.: 196 pp 1–40 DOI: https://doi.org/10.1145/3631410 Published: 12 January 2024

This paper is open access.

Biobattery with a 100-year shelf life

According to an April 18, 2023 news item on ScienceDaily this long-lasting (100 years potentially) biobattery runs on bacteria,

A tiny biobattery that could still work after 100 years has been developed by researchers at Binghamton University, State University of New York.

Last fall [2022], Binghamton University Professor Seokheun “Sean” Choi and his Bioelectronics and Microsystems Laboratory published their research into an ingestible biobattery activated by the Ph factor of the human intestine.

Now, he and PhD student Maryam Rezaie have taken what they learned and incorporated it into new ideas for use outside the body.

A new study in the journal Small, which covers nanotechnology, shares the results from using spore-forming bacteria similar to the previous ingestible version to create a device that potentially would still work after 100 years.

An April 12, 2023 Binghamton University news release (also on EurekAlert but published April 18, 2023) by Chris Kocher, which originated the news item, highlights the researcher’s perspective on this work,

“The overall objective is to develop a microbial fuel cell that can be stored for a relatively long period without degradation of biocatalytic activity and also can be rapidly activated by absorbing moisture from the air,” said Choi, a faculty member in the Department of Electrical and Computer Engineering at the Thomas J. Watson College of Engineering and Applied Science.

“We wanted to make these biobatteries for portable, storable and on-demand power generation capabilities,” Choi said. “The problem is, how can we provide the long-term storage of bacteria until used? And if that is possible, then how would you provide on-demand battery activation for rapid and easy power generation? And how would you improve the power?”

The dime-sized fuel cell was sealed with a piece of Kapton tape, a material that can withstand temperatures from -500 to 750 degrees Fahrenheit. When the tape was removed and moisture allowed in, the bacteria mixed with a chemical germinant that encouraged the microbes to produce spores. The energy from that reaction produced enough to power an LED, a digital thermometer or a small clock.

Heat activation of the bacterial spores cut the time to full power from 1 hour to 20 minutes, and increasing the humidity led to higher electrical output. After a week of storage at room temperature, there was only a 2% drop in power generation.

The study is funded by the [US] Office of Naval Research, and it’s easy to imagine the military applications for a power source that could be deployed on the battlefield or in remote locations. However, there would be plenty of civilian uses for such a fuel cell, too.

While these are all good results, Choi knows that a fuel cell like this needs to power up more quickly and produce more voltage to become a viable alternative to traditional batteries.

“I think this is a good start,” he said. “Hopefully, we can make a commercial product using these ideas.”

Here’s a link to and a citation for the paper,

Moisture-Enabled Germination of Heat-Activated Bacillus Endospores for Rapid and Practical Bioelectricity Generation: Toward Portable, Storable Bacteria-Powered Biobatteries by Maryam Rezaie, Seokheun Choi. Small, Online Version of Record before inclusion in an issue 2301135 DOI: https://doi.org/10.1002/smll.202301135 First published online: 18 March 2023

This paper is behind a paywall.

Spinach could help power fuel cells.

By Source (WP:NFCC#4), Fair use, https://en.wikipedia.org/w/index.php?curid=65303730

I was surprised to see a reference to the cartoon character, Popeye, in the headline (although it’s not carried forward into the text) for this October 5, 2020 news item on ScienceDaily about research into making fuel cells more efficient,

Spinach: Good for Popeye and the planet

“Eat your spinach,” is a common refrain from many people’s childhoods. Spinach, the hearty, green vegetable chock full of nutrients, doesn’t just provide energy in humans. It also has potential to help power fuel cells, according to a new paper by researchers in AU’s Department of Chemistry. Spinach, when converted from its leafy, edible form into carbon nanosheets, acts as a catalyst for an oxygen reduction reaction in fuel cells and metal-air batteries.

An October 5, 2020 American University news release (also on EurekAlert) by Rebecca Basu, which originated the news item, provides more detail about the research,

An oxygen reduction reaction is one of two reactions in fuel cells and metal-air batteries and is usually the slower one that limits the energy output of these devices. Researchers have long known that certain carbon materials can catalyze the reaction. But those carbon-based catalysts don’t always perform as good or better than the traditional platinum-based catalysts. The AU researchers wanted to find an inexpensive and less toxic preparation method for an efficient catalyst by using readily available natural resources. They tackled this challenge by using spinach.

“This work suggests that sustainable catalysts can be made for an oxygen reduction reaction from natural resources,” said Prof. Shouzhong Zou, chemistry professor at AU and the paper’s lead author. “The method we tested can produce highly active, carbon-based catalysts from spinach, which is a renewable biomass. In fact, we believe it outperforms commercial platinum catalysts in both activity and stability. The catalysts are potentially applicable in hydrogen fuel cells and metal-air batteries.” Zou’s former post-doctoral students Xiaojun Liu and Wenyue Li and undergraduate student Casey Culhane are the paper’s co-authors.

Catalysts accelerate an oxygen reduction reaction to produce sufficient current and create energy. Among the practical applications for the research are fuel cells and metal-air batteries, which power electric vehicles and types of military gear. Researchers are making progress in the lab and in prototypes with catalysts derived from plants or plant products such as cattail grass or rice. Zou’s work is the first demonstration using spinach as a material for preparing oxygen reduction reaction-catalysts. Spinach is a good candidate for this work because it survives in low temperatures, is abundant and easy to grow, and is rich in iron and nitrogen that are essential for this type of catalyst.

Zou and his students created and tested the catalysts, which are spinach-derived carbon nanosheets. Carbon nanosheets are like a piece of paper with the thickness on a nanometer scale, a thousand times thinner than a piece of human hair. To create the nanosheets, the researchers put the spinach through a multi-step process that included both low- and high-tech methods, including washing, juicing and freeze-drying the spinach, manually grinding it into a fine powder with a mortar and pestle, and “doping” the resulting carbon nanosheet with extra nitrogen to improve its performance. The measurements showed that the spinach-derived catalysts performed better than platinum-based catalysts that can be expensive and lose their potency over time.

The next step for the researchers is to put the catalysts from the lab simulation into prototype devices, such as hydrogen fuel cells, to see how they perform and to develop catalysts from other plants. Zou would like to also improve sustainability by reducing the energy consumption needed for the process.

Here’s a link to and a citation for the paper,

Spinach-Derived Porous Carbon Nanosheets as High-Performance Catalysts for Oxygen Reduction Reaction by Xiaojun Liu, Casey Culhane, Wenyue Li, and Shouzhong Zou. ACS Omega 2020, 5, 38, 24367–24378 DOI: https://doi.org/10.1021/acsomega.0c02673 Publication Date:September 15, 2020 Copyright © 2020 American Chemical Society

This paper appears to be open access.

Seaweed supercapacitors

I like munching on seaweed from time to time but it seems that seaweed may be more than just a foodstuff according to an April 5, 2017 news item on Nanowerk,

Seaweed, the edible algae with a long history in some Asian cuisines, and which has also become part of the Western foodie culture, could turn out to be an essential ingredient in another trend: the development of more sustainable ways to power our devices. Researchers have made a seaweed-derived material to help boost the performance of superconductors, lithium-ion batteries and fuel cells.

The team will present the work today [April 5, 2017] at the 253rd National Meeting & Exposition of the American Chemical Society (ACS). ACS, the world’s largest scientific society, is holding the meeting here through Thursday. It features more than 14,000 presentations on a wide range of science topics.

An April 5, 2017 American Chemical Society news release on EurekAlert), which originated the news item, gives more details about the presentation,

“Carbon-based materials are the most versatile materials used in the field of energy storage and conversion,” Dongjiang Yang, Ph.D., says. “We wanted to produce carbon-based materials via a really ‘green’ pathway. Given the renewability of seaweed, we chose seaweed extract as a precursor and template to synthesize hierarchical porous carbon materials.” He explains that the project opens a new way to use earth-abundant materials to develop future high-performance, multifunctional carbon nanomaterials for energy storage and catalysis on a large scale.

Traditional carbon materials, such as graphite, have been essential to creating the current energy landscape. But to make the leap to the next generation of lithium-ion batteries and other storage devices, an even better material is needed, preferably one that can be sustainably sourced, Yang says.

With these factors in mind, Yang, who is currently at Qingdao University (China), turned to the ocean. Seaweed is an abundant algae that grows easily in salt water. While Yang was at Griffith University in Australia, he worked with colleagues at Qingdao University and at Los Alamos National Laboratory in the U.S. to make porous carbon nanofibers from seaweed extract. Chelating, or binding, metal ions such as cobalt to the alginate molecules resulted in nanofibers with an “egg-box” structure, with alginate units enveloping the metal ions. This architecture is key to the material’s stability and controllable synthesis, Yang says.

Testing showed that the seaweed-derived material had a large reversible capacity of 625 milliampere hours per gram (mAhg-1), which is considerably more than the 372 mAhg-1 capacity of traditional graphite anodes for lithium-ion batteries. This could help double the range of electric cars if the cathode material is of equal quality. The egg-box fibers also performed as well as commercial platinum-based catalysts used in fuel-cell technologies and with much better long-term stability. They also showed high capacitance as a superconductor material at 197 Farads per gram, which could be applied in zinc-air batteries and supercapacitors. The researchers published their initial results in ACS Central Science in 2015 and have since developed the materials further.

For example, building on the same egg-box structure, the researchers say they have suppressed defects in seaweed-based, lithium-ion battery cathodes that can block the movement of lithium ions and hinder battery performance. And recently, they have developed an approach using red algae-derived carrageenan and iron to make a porous sulfur-doped carbon aerogel with an ultra-high surface area. The structure could be a good candidate to use in lithium-sulfur batteries and supercapacitors.

More work is needed to commercialize the seaweed-based materials, however. Yang says currently more than 20,000 tons of alginate precursor can be extracted from seaweed per year for industrial use. But much more will be required to scale up production.

Here’s an image representing the research,

Scientists have created porous ‘egg-box’ structured nanofibers using seaweed extract. Credit: American Chemical Society

I’m not sure that looks like an egg-box but I’ll take their word for it.

A treasure trove of molecule and battery data released to the public

Scientists working on The Materials Project have taken the notion of open science to their hearts and opened up access to their data according to a June 9, 2016 news item on Nanowerk,

The Materials Project, a Google-like database of material properties aimed at accelerating innovation, has released an enormous trove of data to the public, giving scientists working on fuel cells, photovoltaics, thermoelectrics, and a host of other advanced materials a powerful tool to explore new research avenues. But it has become a particularly important resource for researchers working on batteries. Co-founded and directed by Lawrence Berkeley National Laboratory (Berkeley Lab) scientist Kristin Persson, the Materials Project uses supercomputers to calculate the properties of materials based on first-principles quantum-mechanical frameworks. It was launched in 2011 by the U.S. Department of Energy’s (DOE) Office of Science.

A June 8, 2016 Berkeley Lab news release, which originated the news item, provides more explanation about The Materials Project,

The idea behind the Materials Project is that it can save researchers time by predicting material properties without needing to synthesize the materials first in the lab. It can also suggest new candidate materials that experimentalists had not previously dreamed up. With a user-friendly web interface, users can look up the calculated properties, such as voltage, capacity, band gap, and density, for tens of thousands of materials.

Two sets of data were released last month: nearly 1,500 compounds investigated for multivalent intercalation electrodes and more than 21,000 organic molecules relevant for liquid electrolytes as well as a host of other research applications. Batteries with multivalent cathodes (which have multiple electrons per mobile ion available for charge transfer) are promising candidates for reducing cost and achieving higher energy density than that available with current lithium-ion technology.

The sheer volume and scope of the data is unprecedented, said Persson, who is also a professor in UC Berkeley’s Department of Materials Science and Engineering. “As far as the multivalent cathodes, there’s nothing similar in the world that exists,” she said. “To give you an idea, experimentalists are usually able to focus on one of these materials at a time. Using calculations, we’ve added data on 1,500 different compositions.”

While other research groups have made their data publicly available, what makes the Materials Project so useful are the online tools to search all that data. The recent release includes two new web apps—the Molecules Explorer and the Redox Flow Battery Dashboard—plus an add-on to the Battery Explorer web app enabling researchers to work with other ions in addition to lithium.

“Not only do we give the data freely, we also give algorithms and software to interpret or search over the data,” Persson said.

The Redox Flow Battery app gives scientific parameters as well as techno-economic ones, so battery designers can quickly rule out a molecule that might work well but be prohibitively expensive. The Molecules Explorer app will be useful to researchers far beyond the battery community.

“For multivalent batteries it’s so hard to get good experimental data,” Persson said. “The calculations provide rich and robust benchmarks to assess whether the experiments are actually measuring a valid intercalation process or a side reaction, which is particularly difficult for multivalent energy technology because there are so many problems with testing these batteries.”

Here’s a screen capture from the Battery Explorer app,

The Materials Project’s Battery Explorer app now allows researchers to work with other ions in addition to lithium.

The Materials Project’s Battery Explorer app now allows researchers to work with other ions in addition to lithium. Courtesy: The Materials Project

The news release goes on to describe a new discovery made possible by The Materials Project (Note: A link has been removed),

Together with Persson, Berkeley Lab scientist Gerbrand Ceder, postdoctoral associate Miao Liu, and MIT graduate student Ziqin Rong, the Materials Project team investigated some of the more promising materials in detail for high multivalent ion mobility, which is the most difficult property to achieve in these cathodes. This led the team to materials known as thiospinels. One of these thiospinels has double the capacity of the currently known multivalent cathodes and was recently synthesized and tested in the lab by JCESR researcher Linda Nazar of the University of Waterloo, Canada.

“These materials may not work well the first time you make them,” Persson said. “You have to be persistent; for example you may have to make the material very phase pure or smaller than a particular particle size and you have to test them under very controlled conditions. There are people who have actually tried this material before and discarded it because they thought it didn’t work particularly well. The power of the computations and the design metrics we have uncovered with their help is that it gives us the confidence to keep trying.”

The researchers were able to double the energy capacity of what had previously been achieved for this kind of multivalent battery. The study has been published in the journal Energy & Environmental Science in an article titled, “A High Capacity Thiospinel Cathode for Mg Batteries.”

“The new multivalent battery works really well,” Persson said. “It’s a significant advance and an excellent proof-of-concept for computational predictions as a valuable new tool for battery research.”

Here’s a link to and a citation for the paper,

A high capacity thiospinel cathode for Mg batteries by Xiaoqi Sun, Patrick Bonnick, Victor Duffort, Miao Liu, Ziqin Rong, Kristin A. Persson, Gerbrand Ceder and  Linda F. Nazar. Energy Environ. Sci., 2016, Advance Article DOI: 10.1039/C6EE00724D First published online 24 May 2016

This paper seems to be behind a paywall.

Getting back to the news release, there’s more about The Materials Project in relationship to its membership,

The Materials Project has attracted more than 20,000 users since launching five years ago. Every day about 20 new users register and 300 to 400 people log in to do research.

One of those users is Dane Morgan, a professor of engineering at the University of Wisconsin-Madison who develops new materials for a wide range of applications, including highly active catalysts for fuel cells, stable low-work function electron emitter cathodes for high-powered microwave devices, and efficient, inexpensive, and environmentally safe solar materials.

“The Materials Project has enabled some of the most exciting research in my group,” said Morgan, who also serves on the Materials Project’s advisory board. “By providing easy access to a huge database, as well as tools to process that data for thermodynamic predictions, the Materials Project has enabled my group to rapidly take on materials design projects that would have been prohibitive just a few years ago.”

More materials are being calculated and added to the database every day. In two years, Persson expects another trove of data to be released to the public.

“This is the way to reach a significant part of the research community, to reach students while they’re still learning material science,” she said. “It’s a teaching tool. It’s a science tool. It’s unprecedented.”

Supercomputing clusters at the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility hosted at Berkeley Lab, provide the infrastructure for the Materials Project.

Funding for the Materials Project is provided by the Office of Science (US Department of Energy], including support through JCESR [Joint Center for Energy Storage Research].

Happy researching!

Enzymatic fuel cells with ultrasmall gold nanocluster

Scientists at the US Department of Energy’s Los Alamos National Laboratory have developed a DNA-templated gold nanocluster (AuNC) for more efficient biofuel cell design (Note: A link has been removed). From a Sept. 24, 2015 news item on ScienceDaily,

With fossil-fuel sources dwindling, better biofuel cell design is a strong candidate in the energy field. In research published in the Journal of the American Chemical Society (“A Hybrid DNA-Templated Gold Nanocluster For Enhanced Enzymatic Reduction of Oxygen”), Los Alamos researchers and external collaborators synthesized and characterized a new DNA-templated gold nanocluster (AuNC) that could resolve a critical methodological barrier for efficient biofuel cell design.

Here’s an image illustrating the DNA-templated gold nanoclusters,

Caption: Gold nanoclusters (~1 nm) are efficient mediators of electron transfer between co-self-assembled enzymes and carbon nanotubes in an enzyme fuel cell. The efficient electron transfer from this quantized nano material minimizes the energy waste and improves the kinetics of the oxygen reduction reaction, toward a more efficient fuel cell cycle. Credit: Los Alamos National Laboratory

Caption: Gold nanoclusters (~1 nm) are efficient mediators of electron transfer between co-self-assembled enzymes and carbon nanotubes in an enzyme fuel cell. The efficient electron transfer from this quantized nano material minimizes the energy waste and improves the kinetics of the oxygen reduction reaction, toward a more efficient fuel cell cycle.
Credit: Los Alamos National Laboratory

A Sept. 24, 2015 Los Alamos National Laboratory news release, which originated the news item, provides more details,

“Enzymatic fuel cells and nanomaterials show great promise and as they can operate under environmentally benign neutral pH conditions, they are a greener alternative to existing alkaline or acidic fuel cells, making them the subject of worldwide research endeavors,” said Saumen Chakraborty, a scientist on the project. “Our work seeks to boost electron transfer efficiency, creating a potential candidate for the development of cathodes in enzymatic fuel cells.”

Ligands, molecules that bind to a central metal atom, are necessary to form stable nanoclusters. For this study, the researchers chose single-stranded DNA as the ligand, as DNA is a natural nanoscale material having high affinity for metal cations and can be used to assembly the cluster to other nanoscale material such as carbon nanotubes.

In enzymatic fuel cells, fuel is oxidized on the anode, while oxygen reduction reactions take place on the cathode, often using multi copper oxidases. Enzymatic fuel cell performance depends critically on how effectively the enzyme active sites can accept and donate electrons from the electrode by direct electron transfer (ET). However, the lack of effective ET between the enzyme active sites, which are usually buried ~10Å from their surface, and the electrode is a major barrier to their development. Therefore, effective mediators of this electron transfer are needed.

The team developed a new DNA-templated gold nanocluster (AuNC) that enhanced electron transfer. This novel role of the AuNC as enhancer of electron transfer at the enzyme-electrode interface could be effective for cathodes in enzymatic fuel cells, thus removing a critical methodological barrier for efficient biofuel cell design.

Possessing many unique properties due to their discrete electron state distributions, metal nanoclusters (<1.5 nm diameter; ~2-144 atoms of gold, silver, platinum, or copper) show application in many fields.

Hypothesizing that due to the ultra-small size (the clusters are ~7 atoms, ~0.9 nm in diameter), and unique electrochemical properties, the AuNC can facilitate electron transfer to an oxygen-reduction reaction enzyme-active site and therefore, lower the overpotential of the oxygen reaction. Overpotential is the extra amount of energy required to drive an electrochemical reaction.

Ideally, it is desirable that all electrochemical reactions have minimal to no overpotential, but in reality they all have some. Therefore, to design an efficient electrocatalyst (for reduction or oxidation) we want to design it so that the reaction can proceed with a minimal amount of extra, applied energy.

When self assembled with bilirubin oxidase and carbon nanotubes, the AuNC acts to enhance the electron transfer, and it lowers the overpotential of oxygen reduction by a significant ~15 mV (as opposed to ~1-2 mV observed using other types of mediators) compared to the enzyme alone. The AuNC also causes significant enhancement of electrocatalytic current densities. Proteins are electronically insulating (they are complex, greasy and large), so the use of carbon nanotubes helps the enzyme stick to the electrode as well as to facilitate electron transfer.

Although gold nanoclusters have been used in chemical catalysis, this is the first time that we demonstrate they can also act as electron relaying agents to enzymatic oxygen reduction reaction monitored by electrochemistry.

Finally, the presence of AuNC does not perturb the mechanism of enzymatic O2 reduction. Such unique application of AuNC as facilitator of ET by improving thermodynamics and kinetics of O2 reduction is unprecedented.

Here’s a link to and a citation for the paper,

A Hybrid DNA-Templated Gold Nanocluster For Enhanced Enzymatic Reduction of Oxygen by Saumen Chakraborty, Sofia Babanova, Reginaldo C. Rocha, Anil Desireddy, Kateryna Artyushkova, Amy E. Boncella, Plamen Atanassov, and Jennifer S. Martinez. J. Am. Chem. Soc., 2015, 137 (36), pp 11678–11687 DOI: 10.1021/jacs.5b05338 Publication Date (Web): August 19, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

Brushing your way to nanofibres

The scientists are using what looks like a hairbrush to create nanofibres ,

Figure 2: Brush-spinning of nanofibers. (Reprinted with permission by Wiley-VCH Verlag)) [downloaded from http://www.nanowerk.com/spotlight/spotid=41398.php]

Figure 2: Brush-spinning of nanofibers. (Reprinted with permission by Wiley-VCH Verlag)) [downloaded from http://www.nanowerk.com/spotlight/spotid=41398.php]

A Sept. 23, 2015 Nanowerk Spotlight article by Michael Berger provides an in depth look at this technique (developed by a joint research team of scientists from the University of Georgia, Princeton University, and Oxford University) which could make producing nanofibers for use in scaffolds (tissue engineering and other applications) more easily and cheaply,

Polymer nanofibers are used in a wide range of applications such as the design of new composite materials, the fabrication of nanostructured biomimetic scaffolds for artificial bones and organs, biosensors, fuel cells or water purification systems.

“The simplest method of nanofiber fabrication is direct drawing from a polymer solution using a glass micropipette,” Alexander Tokarev, Ph.D., a Research Associate in the Nanostructured Materials Laboratory at the University of Georgia, tells Nanowerk. “This method however does not scale up and thus did not find practical applications. In our new work, we introduce a scalable method of nanofiber spinning named touch-spinning.”

James Cook in a Sept. 23, 2015 article for Materials Views provides a description of the technology,

A glass rod is glued to a rotating stage, whose diameter can be chosen over a wide range of a few centimeters to more than 1 m. A polymer solution is supplied, for example, from a needle of a syringe pump that faces the glass rod. The distance between the droplet of polymer solution and the tip of the glass rod is adjusted so that the glass rod contacts the polymer droplet as it rotates.

Following the initial “touch”, the polymer droplet forms a liquid bridge. As the stage rotates the bridge stretches and fiber length increases, with the diameter decreasing due to mass conservation. It was shown that the diameter of the fiber can be precisely controlled down to 40 nm by the speed of the stage rotation.

The method can be easily scaled-up by using a round hairbrush composed of 600 filaments.

When the rotating brush touches the surface of a polymer solution, the brush filaments draw many fibers simultaneously producing hundred kilometers of fibers in minutes.

The drawn fibers are uniform since the fiber diameter depends on only two parameters: polymer concentration and speed of drawing.

Returning to Berger’s Spotlight article, there is an important benefit with this technique,

As the team points out, one important aspect of the method is the drawing of single filament fibers.

These single filament fibers can be easily wound onto spools of different shapes and dimensions so that well aligned one-directional, orthogonal or randomly oriented fiber meshes with a well-controlled average mesh size can be fabricated using this very simple method.

“Owing to simplicity of the method, our set-up could be used in any biomedical lab and facility,” notes Tokarev. “For example, a customized scaffold by size, dimensions and othermorphologic characteristics can be fabricated using donor biomaterials.”

Berger’s and Cook’s articles offer more illustrations and details.

Here’s a link to and a citation for the paper,

Touch- and Brush-Spinning of Nanofibers by Alexander Tokarev, Darya Asheghal, Ian M. Griffiths, Oleksandr Trotsenko, Alexey Gruzd, Xin Lin, Howard A. Stone, and Sergiy Minko. Advanced Materials DOI: 10.1002/adma.201502768ViewFirst published: 23 September 2015

This paper is behind a paywall.

Graphene gains metallic powers after laser-burning

Rice University (Texas, US) researchers have developed a technique for embedding metallic nanoparticles in graphene with the hope of one day replacing platinum catalysts in fuel cells. From an August 20, 2015 news item on ScienceDaily,

Laser-induced graphene, created by the Rice lab of chemist James Tour last year, is a flexible film with a surface of porous graphene made by exposing a common plastic known as polyimide to a commercial laser-scribing beam. The researchers have now found a way to enhance the product with reactive metals.

An August 20, 2015 Rice University news release (also on EurekAlert), which originated the news item, provides further description,

With the discovery, the material that the researchers call “metal oxide-laser induced graphene” (MO-LIG) becomes a new candidate to replace expensive metals like platinum in catalytic fuel-cell applications in which oxygen and hydrogen are converted to water and electricity.

“The wonderful thing about this process is that we can use commercial polymers, with simple inexpensive metal salts added,” Tour said. “We then subject them to the commercial laser scriber, which generates metal nanoparticles embedded in graphene. So much of the chemistry is done by the laser, which generates graphene in the open air at room temperature.

“These composites, which have less than 1 percent metal, respond as ‘super catalysts’ for fuel-cell applications. Other methods to do this take far more steps and require expensive metals and expensive carbon precursors.”

Initially, the researchers made laser-induced graphene with commercially available polyimide sheets. Later, they infused liquid polyimide with boron to produce laser-induced graphene with a greatly increased capacity to store an electrical charge, which made it an effective supercapacitor.

For the latest iteration, they mixed the liquid and one of three concentrations containing cobalt, iron or molybdenum metal salts. After condensing each mixture into a film, they treated it with an infrared laser and then heated it in argon gas for half an hour at 750 degrees Celsius.

That process produced robust MO-LIGs with metallic, 10-nanometer particles spread evenly through the graphene. Tests showed their ability to catalyze oxygen reduction, an essential chemical reaction in fuel cells. Further doping of the material with sulfur allowed for hydrogen evolution, another catalytic process that converts water into hydrogen, Tour said.

“Remarkably, simple treatment of the graphene-molybdenum oxides with sulfur, which converted the metal oxides to metal sulfides, afforded a hydrogen evolution reaction catalyst, underscoring the broad utility of this approach,” he said.

Here’s a link to and a citation for the paper,

In situ Formation of Metal Oxide Nanocrystals Embedded in Laser-Induced Graphene by Ruquan Ye, Zhiwei Peng, Tuo Wang, Yunong Xu, Jibo Zhang, Yilun Li, Lizanne G. Nilewski, Jian Lin, and James M. Tour. ACS Nano, Just Accepted Manuscript DOI: 10.1021/acsnano.5b04138 Publication Date (Web): August 18, 2015
Copyright © 2015 American Chemical Society

This paper is open access provided you have an ACS ID, which is a free registration. ACS is the American Chemical Society.

Graphene not so impermeable after all

I saw the news last week but it took reading Dexter Johnson’s Dec. 2, 2014 post for me to achieve a greater understanding of why graphene’s proton permeability is such a big deal and of the tensions underlying graphene research in the UK.

Let’s start with the news, from a Nov. 26, 2014 news item on Nanowerk (Note: A link has been removed),

Published in the journal Nature (“Proton transport through one-atom-thick crystals”), the discovery could revolutionise fuel cells and other hydrogen-based technologies as they require a barrier that only allow protons – hydrogen atoms stripped off their electrons – to pass through.

In addition, graphene membranes could be used to sieve hydrogen gas out of the atmosphere, where it is present in minute quantities, creating the possibility of electric generators powered by air.

A Nov. 26, 2014 University of Manchester news release, which originated the news item, describes the research in greater detail,

One-atom thick material graphene, first isolated and explored in 2004 by a team at The University of Manchester, is renowned for its barrier properties, which has a number of uses in applications such as corrosion-proof coatings and impermeable packaging.

For example, it would take the lifetime of the universe for hydrogen, the smallest of all atoms, to pierce a graphene monolayer.

Now a group led by Sir Andre Geim tested whether protons are also repelled by graphene. They fully expected that protons would be blocked, as existing theory predicted as little proton permeation as for hydrogen.

Despite the pessimistic prognosis, the researchers found that protons pass through the ultra-thin crystals surprisingly easily, especially at elevated temperatures and if the films were covered with catalytic nanoparticles such as platinum.

The discovery makes monolayers of graphene, and its sister material boron nitride, attractive for possible uses as proton-conducting membranes, which are at the heart of modern fuel cell technology. Fuel cells use oxygen and hydrogen as a fuel and convert the input chemical energy directly into electricity. Without membranes that allow an exclusive flow of protons but prevent other species to pass through, this technology would not exist.

Despite being well-established, fuel-cell technology requires further improvements to make it more widely used. One of the major problems is a fuel crossover through the existing proton membranes, which reduces their efficiency and durability.

The University of Manchester research suggests that the use of graphene or monolayer boron nitride can allow the existing membranes to become thinner and more efficient, with less fuel crossover and poisoning. This can boost competitiveness of fuel cells.

The Manchester group also demonstrated that their one-atom-thick membranes can be used to extract hydrogen from a humid atmosphere. They hypothesise that such harvesting can be combined together with fuel cells to create a mobile electric generator that is fuelled simply by hydrogen present in air.

Marcelo Lozada-Hidalgo, a PhD student and corresponding author of this paper, said: “When you know how it should work, it is a very simple setup. You put a hydrogen-containing gas on one side, apply small electric current and collect pure hydrogen on the other side. This hydrogen can then be burned in a fuel cell.

“We worked with small membranes, and the achieved flow of hydrogen is of course tiny so far. But this is the initial stage of discovery, and the paper is to make experts aware of the existing prospects. To build up and test hydrogen harvesters will require much further effort.”

Dr Sheng Hu, a postdoctoral researcher and the first author in this work, added: “It looks extremely simple and equally promising. Because graphene can be produced these days in square metre sheets, we hope that it will find its way to commercial fuel cells sooner rather than later”.

The work is an international collaboration involving groups from China and the Netherlands who supported theoretical aspects of this research. Marcelo Lozada-Hidalgo is funded by a PhD studentship programme between the National Council of Science and Technology of Mexico and The University of Manchester.

Here’s more about the research and its implications from Dexter Johnson’s Dec. 2, 2014 post on the Nanoclast blog on the IEEE (Institute of Electronics and Electrical Engineers) website (Note: Links have been removed),

This latest development alters the understanding of one of the key properties of graphene: that it is impermeable to all gases and liquids. Even an atom as small as hydrogen would need billions of years for it to pass through the dense electronic cloud of graphene.  In fact, it is this impermeability that has made it attractive for use in gas separation membranes.

But as Geim and his colleagues discovered, in research that was published in the journal Nature, monolayers of graphene and boron nitride are highly permeable to thermal protons under ambient conditions. So hydrogen atoms stripped of their electrons could pass right through the one-atom-thick materials.

The surprising discovery that protons could breach these materials means that that they could be used in proton-conducting membranes (also known as proton exchange membranes), which are central to the functioning of fuel cells. Fuel cells operate through chemical reactions involving hydrogen fuel and oxygen, with the result being electrical energy. The membranes used in the fuel cells are impermeable to oxygen and hydrogen but allow for the passage of protons.

Dexter goes into more detail about hydrogen fuel cells and why this discovery is so exciting. He also provides some insight into the UK’s graphene community (Note: A link has been removed),

While some have been frustrated that Geim has focused his attention on fundamental research rather than becoming more active in the commercialization of graphene, he may have just cracked open graphene’s greatest application possibility to date.

I recommend reading Dexter’s post if you want to learn more about fuel cell technology and the impact this discovery may have.

Richard Van Noorden’s Nov. 27, 2014 article for Nature provides another perspective on this work,

Fuel-cell experts say that the work is proof of principle, but are cautious about its immediate application. Factors such as to how grow a sufficiently clean, large graphene sheet, and its cost and lifetime, would have to be taken into account. “It may or may not be a better membrane for a fuel cell,” says Andrew Herring, a chemical engineer at the Colorado School of Mines in Golden.

Van Noorden also writes about another graphene discovery from last week, which won’t be featured here. Where graphene is concerned I have to draw a line or else this entire blog would be focused on that material alone.

Getting back back to permeability, graphene, and protons, here’s a link to and a citation for the research paper,

Proton transport through one-atom-thick crystals by S. Hu, M. Lozada-Hidalgo, F. C. Wang, A. Mishchenko, F. Schedin, R. R. Nair, E. W. Hill, D. W. Boukhvalov, M. I. Katsnelson, R. A. W. Dryfe, I. V. Grigorieva, H. A. Wu, & A. K. Geim. Nature (2014 doi:10.1038/nature14015 Published online 26 November 2014

This article is behind a paywall.

Loofahs, microbes, and fuel cells

Thank you to whomever wrote this Dec. 4, 2013 news release (h/t to the Dec. 5, 2013 news item on Azonano) for the American Chemical Society (ACS),

Loofahs, best known for their use in exfoliating skin to soft, radiant perfection, have emerged as a new potential tool to advance sustainability efforts on two fronts at the same time: energy and waste. [emphasis mine] The study describes the pairing of loofahs with bacteria to create a power-generating microbial fuel cell (MFC) and appears in the ACS journal Environmental Science & Technology.

The rest of the news release confines itself to information about the researchers and the research,

Shungui Zhou and colleagues note that MFCs, which harness the ability of some bacteria to convert waste into electric power, could help address both the world’s growing waste problem and its need for clean power. Current MFC devices can be expensive and complicated to make. In addition, the holes, or pores, in the cells’ electrodes are often too small for bacteria to spread out in. Recently, researchers have turned to plant materials as a low-cost alternative, but pore size has still been an issue. Loofahs, which come from the fully ripened fruit of loofah plants, are commonly used as bathing sponges. They have very large pores, yet are still inexpensive. That’s why Zhou’s team decided to investigate their potential use in MFCs.

When the scientists put nitrogen-enriched carbon nanoparticles on loofahs and loaded them with bacteria, the resulting MFC performed better than traditional MFCs. “This study introduces a promising method for the fabrication of high-performance anodes from low-cost, sustainable natural materials,” the researchers state.

Here’s a link to and a citation for the paper,

Nanostructured Macroporous Bioanode Based on Polyaniline-Modified Natural Loofah Sponge for High-Performance Microbial Fuel Cells by Yong Yuan, Shungui Zhou, Yi Liu, and Jiahuan Tang. Environ. Sci. Technol., Article ASAP DOI: 10.1021/es404163g Publication Date (Web): November 15, 2013
Copyright © 2013 American Chemical Society

This paper is behind a paywall.