Tag Archives: platinum

Nanoscale snowman and Season’s Greetings

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It’s being described as a ‘jeweled nano-snowman’ but platinum and titanium aren’t my idea of jewels. Still, it’s a cheerful, seasonal greeting.

Courtesy of the University of Birmingham Nanoscale Physics Research Laboratory

Courtesy of the University of Birmingham Nanoscale Physics Research Laboratory

A December 22, 2015 news item on Nanowerk tells more of the story,

Would a jewel-encrusted snowman make the perfect Christmas present? At only 5 nanometres in size, the price might be lower than you think. And it’s functional too, catalysing the splitting of water to make green hydrogen for fuel cells.

A December 22, 2015 University of Birmingham Nanoscale Physics Research Laboratory (NPRL) press release, which originated the news item, provides more detail,

The nanoparticle, as imaged with an aberration-corrected scanning transmission electron microscope, features eyes, nose and mouth of precious-metal platinum clusters embedded in a titanium dioxide face. Each platinum cluster typically contains 30 platinum atoms; within the whole nanoparticle there are approximately 1,680 titanium atoms and 180 platinum atoms. The nano-snowman formed spontaneously from a self-assembled platinum-titanium nanoparticle which was oxidised in air, drawing the titanium atoms out to the surface. The self-assembly occurred in a gas phase, cluster beam condensation source, before size-selection with a mass spectrometer and deposition onto a carbon surface for oxidation and then imaging. The mass of the snowman is 120,000 atomic mass units. Compared with a more conventional pure platinum catalyst particle, the inclusion of the titanium atoms offers two potential benefits: dilution of how much precious platinum is needed to perform the catalysis, and protection of the platinum cores against sintering (i.e. aggregation of the nanoparticles). The shell is porous enough to allow hydrogen through and the particles are functional in the hydrogen evolution reaction. The research was performed at the Nanoscale Physics Research Lab by Caroline Blackmore and Ross Griffin. …

The scientists did a little bit of work adding colour (most of these images are gray on gray), as well as, the holly and berry frame.

Joyeux Noël et Bonne Année or Season’s Greetings!

Combining gold and palladium for catalytic and plasmonic octopods

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Hopefully I did not the change meaning when I made the title for this piece more succinct. In any event, this research comes from the always prolific Rice University in Texas, US (from a Nov. 30, 2015 news item on Nanotechnology Now),

Catalysts are substances that speed up chemical reactions and are essential to many industries, including petroleum, food processing and pharmaceuticals. Common catalysts include palladium and platinum, both found in cars’ catalytic converters. Plasmons are waves of electrons that oscillate in particles, usually metallic, when excited by light. Plasmonic metals like gold and silver can be used as sensors in biological applications and for chemical detection, among others.

Plasmonic materials are not the best catalysts, and catalysts are typically very poor for plasmonics. But combining them in the right way shows promise for industrial and scientific applications, said Emilie Ringe, a Rice assistant professor of materials science and nanoengineering and of chemistry who led the study that appears in Scientific Reports.

“Plasmonic particles are magnets for light,” said Ringe, who worked on the project with colleagues in the U.S., the United Kingdom and Germany. “They couple with light and create big electric fields that can drive chemical processes. By combining these electric fields with a catalytic surface, we could further push chemical reactions. That’s why we’re studying how palladium and gold can be incorporated together.”

The researchers created eight-armed specks of gold and coated them with a gold-palladium alloy. The octopods proved to be efficient catalysts and sensors.

A Nov. 30, 2015 Rice University news release (also on EurekAlert), which originated the news item, expands on the theme,

“If you simply mix gold and palladium, you may end up with a bad plasmonic material and a pretty bad catalyst, because palladium does not attract light like gold does,” Ringe said. “But our particles have gold cores with palladium at the tips, so they retain their plasmonic properties and the surfaces are catalytic.”

Just as important, Ringe said, the team established characterization techniques that will allow scientists to tune application-specific alloys that report on their catalytic activity in real time.

The researchers analyzed octopods with a variety of instruments, including Rice’s new Titan Themis microscope, one of the most powerful electron microscopes in the nation. “We confirmed that even though we put palladium on a particle, it’s still capable of doing everything that a similar gold shape would do. That’s really a big deal,” she said.

“If you shine a light on these nanoparticles, it creates strong electric fields. Those fields enhance the catalysis, but they also report on the catalysis and the molecules present at the surface of the particles,” Ringe said.

The researchers used electron energy loss spectroscopy, cathodoluminescence and energy dispersive X-ray spectroscopy to make 3-D maps of the electric fields produced by exciting the plasmons. They found that strong fields were produced at the palladium-rich tips, where plasmons were the least likely to be excited.

Ringe expects further research will produce multifunctional nanoparticles in a variety of shapes that can be greatly refined for applications. Her own Rice lab is working on a metal catalyst to turn inert petroleum derivatives into backbone molecules for novel drugs.

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

Resonances of nanoparticles with poor plasmonic metal tips by Emilie Ringe, Christopher J. DeSantis, Sean M. Collins, Martial Duchamp, Rafal E. Dunin-Borkowski, Sara E. Skrabalak, & Paul A. Midgley.  Scientific Reports 5, Article number: 17431 (2015)  doi:10.1038/srep17431 Published online: 30 November 2015

This is an open access paper,

Green tech with single atom platinum catalyst?

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There’s something mind boggling to me about the notion of a single atom catalyst. Luckily, an Oct. 5, 2015 news item on Nanowerk describes the research (Note: A link has been removed),

A new generation of platinum-copper catalysts that require very low concentrations of platinum in the form of individual atoms to cleanly and cheaply perform important chemical reactions is reported today by Tufts University researchers in the journal Nature Communications (“Selective hydrogenation of butadiene on platinum copper alloys at the single atom limit”).

An Oct. 9, 2015 Tufts University news release on EurekAlert, which originated the news item, describes the nature of the problem the researchers were trying to resolve and their solution,

Platinum is used as a catalyst in fuel cells, in automobile converters and in the chemical industry because of its remarkable ability to facilitate a wide range of chemical reactions. However, its future potential uses are significantly limited by scarcity and cost, as well as the fact that platinum readily binds with carbon monoxide, which “poisons” the desired reactions, for example in polymer electrolyte membrane (PEM) fuel cells, which are the leading contenders for small-scale and mobile power generation not based on batteries or combustion engines.

The Tufts researchers discovered that dispersing individual, isolated platinum atoms in much less costly copper surfaces can create a highly effective and cost-efficient catalyst for the selective hydrogenation of 1,3 butadiene, a chemical produced by steam cracking of naphtha or by catalytic cracking of gas oil. Butadiene is an impurity in propene streams that must be removed from the stream through hydrogenation in order to facilitate downstream polymer production. The current industrial catalyst for butadiene hydrogenation uses palladium and silver.

Like Sugar in Coffee

Copper, while a relatively cheap metal, is not nearly as catalytically powerful as platinum, noted Professor of Chemistry Charles Sykes, Ph.D., one of the senior authors on the paper. “We wanted to find a way to improve its performance.”

The researchers first conducted surface science experiments to study precisely how platinum and copper metals mix. “We were excited to find that the platinum metal dissolved in copper, just like sugar in hot coffee, all the way down to single atoms. We call such materials single atom alloys,” said Sykes.

The Tufts chemists used a specialized low temperature scanning tunneling microscope to visualize the single platinum atoms and their interaction with hydrogen. “We found that even at temperatures as low as minus 300 degrees F these platinum atoms were capable of splitting hydrogen molecules into atoms, indicating that the platinum atoms would be very good at activating hydrogen for a chemical reaction,” Sykes said.

With that knowledge, Sykes and his fellow chemists turned to long-time Tufts collaborator Maria Flytzani-Stephanopoulos, Ph.D., the Robert and Marcy Haber Endowed Professor in Energy Sustainability at the School of Engineering, to determine which hydrogenation reaction would be most significant for industrial applications. The answer, she said, was butadiene.

The model catalyst performed effectively for that reaction in vacuum conditions in the laboratory, so Flytzani-Stephanopoulos’s team took the study to the next level. They synthesized small quantities of realistic catalysts, such as platinum-copper single atom alloy nanoparticles supported on an alumina substrate, and then tested them under industrial pressure and temperatures.

“To our delight, these catalysts worked very well and their performance was steady for many days,” said Flytzani-Stephanopoulos. “While we had previously shown that palladium would do related reactions in a closed reactor system, this work with platinum is our first demonstration of operation in a flow reactor at industrially relevant conditions. We believe this approach is also applicable to other precious metals if added as minority components in copper.”

Further, the researchers found that the reaction actually became less efficient when they used more platinum, because clusters of platinum atoms have inferior selectivity compared with individual atoms. “In this case, less is more,” said Flytzani-Stephanopoulos, “which is a very good thing.”

Environmental Benefits

Because platinum is at the center of many clean energy and green chemicals production technologies, such as fuel cells, catalytic converters, and value-added chemicals from bio-renewable feedstocks, the new, less expensive platinum-copper catalysts could facilitate broader adoption of such environmentally friendly devices and processes, she added.

The news release goes on to describe this cross-disciplinary partnership,

The work is the latest fruit from a long cross-disciplinary partnership between Sykes and Flytzani-Stephanopoulos.

“Maria and I met more than seven years ago and talked regularly about how to combine our fairly different fields of research into an effective collaboration across the schools of Arts and Sciences and Engineering,” said Sykes. “I had a state-of-the-art microscope that could see and manipulate atoms and molecules, and I wanted to use its unique capabilities to gain insight into industrially important chemical reactions. In the early 2000s, Maria’s group had pioneered the single-atom approach for metals anchored on oxide supports as the exclusive active sites for the water-gas shift reaction to upgrade hydrogen streams for fuel cell use. Catalyst design know-how already existed in her lab. In retrospect, it seems obvious that combining forces would be a ‘natural’ development. Together we embarked on a new direction involving single atom alloys as catalysts for selective hydrogenation reactions. Our microscope was uniquely suited for characterizing the atomic composition of surfaces. We got funding from the National Science Foundation, U.S. Department of Energy and the Tufts Collaborates initiative to pursue this new area of research.”

Sykes and Flytzani-Stephanopoulos have used this approach to design a variety of single atom alloy catalysts that have, in the last two years, sparked international interest.

“Traditionally catalyst development happens by trial and error and screening many materials,” said Flytzani-Stephanopoulos. “In this study we took a fundamental approach to understanding the atomic scale structure and properties of single atom alloy surfaces and then applied this knowledge to develop a working catalyst. Armed with this knowledge, we are now ready to compare the stability of these single atom alloy catalysts to single atom catalysts supported on various oxide or carbon surfaces. This may give us very useful criteria for industrial catalyst design.”

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

Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit by Felicia R. Lucci, Jilei Liu, Matthew D. Marcinkowski, Ming Yang, Lawrence F. Allard, Maria Flytzani-Stephanopoulos, & E. Charles H. Sykes. Nature Communications 6, Article number: 8550 doi:10.1038/ncomms9550 Published 09 October 2015

This is an open access paper.

Graphene gains metallic powers after laser-burning

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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.

Platinum catalysts and their shortcomings

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The problem boils down to the fact that platinum isn’t cheap and so US Dept. of Energy research laboratories are looking for alternatives to or ways of making more efficient use of platinum according to a June 16, 2015 news item on Nanowerk,

Visions of dazzling engagement rings may pop to mind when platinum is mentioned, but a significant share of the nearly half a million pounds of the rare metalExternal link [sic] mined each year ends up in vehicle emission systems and chemical manufacturing plants. The silvery white metal speeds up or enhances reactions, a role scientists call serving as a catalyst, and platinum is fast and efficient performing this function.

Because of its outstanding performance as a catalyst, platinum plays a major role in fuel cells. Inside a fuel cell, tiny platinum particles break apart hydrogen fuel to create electricity. Leftover protons are combined with oxygen ions to create pure water.

Fuel cells could let scientists turn wind into fuel. Right now, electricity generated by wind turbines is not stored. If that energy could be converted into hydrogen to power fuel cells, it would turn a sporadic source into a continuous one.

The problem is the platinum – a scarce and costly metal. Scientists funded by the U.S. Department of Energy’s Office of Science are seeing if something more readily available, such as iron or nickel, could catalyze the reaction.

But, earth-abundant metals cannot simply be used in place of platinum and other rare metals. Each metal works differently at the atomic level. It takes basic research to understand the interactions and use that knowledge to create the right catalysts.

A June 15, 2015 US Department of Energy Office of Science news release, which originated the news item, describes various efforts,

At the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, scientists are gaining new understanding of catalysts based on common metals and how they move protons, the positively charged, oft-ignored counterpart to the electron.

Center Director Morris Bullock and his colleagues showed that protons’ ability to move through the catalyst greatly influences the catalyst’s speed and efficiency. Protons move via relays — clusters of atoms that convey protons to or from the active site of catalysts, where the reaction of interest occurs. The constitution, placement, and number of relays can let a reaction zip along or grind to a halt. Bullock and his colleagues are creating “design guidelines” for building relays.

Further, the team is expanding the guidelines to examine proton movement related to the solutions and surfaces where the catalyst resides. For example, matching the proton-donating abilityExternal link [sic] of a nickel-based catalyst to that of the surrounding liquid, much like matching your clothing choice with the event you’re attending, eases protons’ travels. The benefit? Speed. A coordinated catalyst pumped out 96,000 hydrogen molecules a second — compared to just 27,000 molecules a second without the adjustment.

This and other research at the Energy Frontier Research Center is funded by the DOE Office of Science’s Office of Basic Energy Sciences. The Center is led by Pacific Northwest National Laboratory.

At two other labs, research shows how changing the catalyst’s superstructure, which contains the proton relays and wraps around the active site, can also increase the speed of the reaction. Led by Argonne National Lab’s Vojislav Stamenkovic and Berkeley Lab’s Peidong Yang, researchers created hollow platinum and nickel nanoparticles, a thousand times smaller in diameter than a human hair. The 12-sided particles split oxygen molecules into charged oxygen ions, a reaction that’s needed in fuel cells. The new catalyst is far more active and uses far less platinum than conventional platinum-carbon catalysts.

Building the catalysts begins with tiny structures made of platinum and nickel held in solution. Oxygen from the air dissolves into the liquid and selectively etches away some of the nickel atoms. The result is a hollow framework with a highly active platinum skin over the surface. The open design of the catalyst allows the oxygen to easily access the platinum. The new catalyst has a 36-fold increase in activity compared to traditional platinum–carbon catalysts. Further, the new hollow structure continues to work far longer in operating fuel cells than traditional catalysts.

I think we’re entering the ‘slow’ season newswise so there are likely to be more of these ’roundup’ pieces being circulated in the online nanosciencesphere and, consequently, here. too.

Eco-friendly nitrogen-doped graphene nanoplatelets from South Korea

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South Korean researchers from Ulsan National Institute of Science and Technology (UNIST) have devised a new technique to fix nitrogen to graphene, from the July 24, 2013 news item on Azonano,

A simple, low-cost and eco-friendly method of creating nitrogen-doped graphene nanoplatelets (NGnPs), which could be used in dye-sensitized solar cells and fuel cells, is published in Scientific Reports today.

The work, carried out at Ulsan National Institute of Science and Technology (UNIST) in South Korea, could be a step towards replacing conventional platinum (Pt)-based catalysts for energy conversion.

The UNIST July 23, 2013 news release by Eunhee Song, which originated the news item, provides some context for why the technique is exciting interest,

The search for economically viable alternatives to fossil fuels has attracted attention among energy communities because of increasing energy prices and climate change. Solar cells and fuel cells are to be promising alternatives, but Pt-based (platinum-based) electrodes are expensive and susceptible to environmental damage.

Nitrogen fixation is where nitrogen (N2) in the atmosphere is converted into ammonia (NH3). Fixation processes free up nitrogen atoms from their diatomic form to be used in other ways, but nitrogen does not easily react with other chemicals to form new compounds.

The most common method of industrial nitrogen fixation is the Harber-Bosch process, which requires extremely harsh conditions, 200 atm of pressure and 400 °C of temperature.

The UNIST team previously reported that dry ball-milling can efficiently produce chemically modified graphene particles in large quantities*. This research, in Scientific Reports, presents another innovation to improve the materials. Along the way, the research team discovered a novel nitrogen fixation process.

They focus on modifications with nitrogen, developing a technique with direct nitrogen fixation, carbon-nitrogen bond formation, at the broken edges of graphite frameworks using ball-milling graphite in the presence of nitrogen gas.

In my search for this latest paper I found an earlier piece of work based on a wet-chemical reaction and published in the Journal of the American Chemical Society,

Nitrogen-Doped Graphene Nanoplatelets from Simple Solution Edge-Functionalization for n-Type Field-Effect Transistors by Dong Wook Chang, Eun Kwang Lee, Eun Yeob Park, Hojeong Yu, Hyun-Jung Choi, In-Yup Jeon, Gyung-Joo Sohn, Dongbin Shin, Noejung Park, Joon Hak Oh, Liming Dai, and Jong-Beom Baek. J. Am. Chem. Soc., 2013, 135 (24), pp 8981–8988 DOI: 10.1021/ja402555n Publication Date (Web): May 27, 2013
Copyright © 2013 American Chemical Society

That paper is behind a paywall while this latest work featuring a ‘dry’ technique is open access,

Direct nitrogen fixation at the edges of graphene nanoplatelets as efficient electrocatalysts for energy conversion by In-Yup Jeon, Hyun-Jung Choi, Myung Jong Ju, In Taek Choi, Kimin Lim, Jaejung Ko, Hwan Kyu Kim, Jae Cheon Kim, Jae-Joon Lee, Dongbin Shin, Sun-Min Jung, Jeong-Min Seo, Min-Jung Kim, Noejung Park, Liming Dai, & Jong-Beom Baek. Scientific Reports 3, Article number: 2260 doi:10.1038/srep02260 Published 23 July 2013

This team has been quite prolific recently. I last mentioned them in a June 7, 2013 posting highlighting another iteration of this ‘dry’ technique.

Canadian and Japanese researchers create new technique for using iron nanoparticles in greener hydrogenation process

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McGill University’s Audrey Moores and her team’s latest green chemistry work with researchers at RIKEN (The Institute of Physical and Chemical Research, Wako, Japan) and the Institute for Molecular Science (Okazaki, Japan) is featured in a June 27, 2013 news item on Nanowerk,

Researchers from McGill University, RIKEN (The Institute of Physical and Chemical Research, Wako, Japan) and the Institute for Molecular Science (Okazaki, Japan) have discovered a way to make the widely used chemical process of hydrogenation more environmentally friendly – and less expensive.

Hydrogenation is a chemical process used in a wide range of industrial applications, from food products, such as margarine, to petrochemicals and pharmaceuticals. The process typically involves the use of heavy metals, such as palladium or platinum, to catalyze the chemical reaction. While these metals are very efficient catalysts, they are also non-renewable, costly, and subject to sharp price fluctuations on international markets.

Because these metals are also toxic, even in small quantities, they also raise environmental and safety concerns. Pharmaceutical companies, for example, must use expensive purification methods to limit residual levels of these elements in pharmaceutical products. Iron, by contrast, is both naturally abundant and far less toxic than heavy metals.

Previous work by other researchers has shown that iron nanoparticles — tiny pieces of metallic iron — can be used to activate the hydrogenation reaction. Iron, however, has a well-known drawback: it rusts in the presence of oxygen or water. When rusted, iron nanoparticles stop acting as hydrogenation catalysts. This problem, which occurs with so much as trace quantities of water, has prevented iron nanoparticles from being used in industry.

The June 27, 2013 McGill University news release on EurekAlert, which originated the news item, provides details about the new technique,

The key to this new method is to produce the particles directly inside a polymer matrix, composed of amphiphilic polymers based on polystyrene and polyethylene glycol. The polymer acts as a wrapping film that protects the iron surface from rusting in the presence of water, while allowing the reactants to reach the water and react.

This innovation enabled the researchers to use iron nanoparticles as catalyst in a flow system, raising the possibility that iron could be used to replace platinum-series metals for hydrogenation under industrial conditions.

“Our research is now focused on achieving a better understanding of how the polymers are protecting the surface of the iron from water, while at the same time allowing the iron to interact with the substrate,” says Audrey Moores, an assistant professor of chemistry at McGill and co-corresponding author of the paper.

…

“The approach we have developed through this collaboration could lead to more sustainable industrial processes,” says Prof. Uozumi [Prof. Yasuhiro Uozumi of Riken]. “This technique provides a system in which the reaction can happen over and over with the same small amount of a catalytic material, and it enables it to take place in almost pure water — the green solvent par excellence.”

I last wrote about greener chemistry and iron nanoparticles in a March 28, 2012 posting concerning some work at the University of Toronto while the last time McGill, green chemistry, and Audrey Moores were mentioned here was in a Jan. 10, 2011 posting concerning ‘nanomagnetics.

For those who are interested in this latest work from McGill, here’s a link to and a citation for the published paper,

Highly efficient iron(0) nanoparticle-catalyzed hydrogenation in water in flow by Reuben Hudson, Go Hamasaka, Takao Osako, Yoichi M. A. Yamada, Chao-Jun Li, Yasuhiro Uozumi, and Audrey Moores.
Green Chem., 2013, Advance Article DOI: 10.1039/C3GC40789F

First published online 27 Jun 2013

This paper is behind a paywall.

Phyto-mining and environmental remediation flower in the United Kingdom

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Researchers on a £3 million research programme called “Cleaning Land for Wealth” (CL4W) are confident they’ll be able to use flowers and plants to clean soil of poisonous materials (environmental remediation) and to recover platinum (phyto-mining). From the Nov. 21, 2012 news item on Nanowerk,

A consortium of researchers led by WMG (Warwick Manufacturing Group) at the University of Warwick are to embark on a £3 million research programme called “Cleaning Land for Wealth” (CL4W), that will use a common class of flower to restore poisoned soils while at the same time producing perfectly sized and shaped nano sized platinum and arsenic nanoparticles for use in catalytic convertors, cancer treatments and a range of other applications.

The Nov. 20, 2012 University of Warwick news release, which originated the news item, describes both how CL4W came together and how it produced an unintended project benefit,

A “Sandpit” exercise organised by the Engineering and Physical Sciences Research Council (EPSRC) allowed researchers from WMG (Warwick Manufacturing group) at the University of Warwick, Newcastle University, The University of Birmingham, Cranfield University and the University of Edinburgh to come together and share technologies and skills to come up with an innovative multidisciplinary research project that could help solve major technological and environmental challenges.

The researchers pooled their knowledge of how to use plants and bacteria to soak up particular elements and chemicals and how to subsequently harvest, process and collect that material. They have devised an approach to demonstrate the feasibility in which they are confident that they can use common classes of flower and plants (such as Alyssum), to remove poisonous chemicals such as arsenic and platinum from polluted land and water courses potentially allowing that land to be reclaimed and reused.

That in itself would be a significant achievement, but as the sandpit progressed the researchers found that jointly they had the knowledge to achieve much more than just cleaning up the land.

As lead researcher on the project Professor Kerry Kirwan from WMG at the University of Warwick explained:

“The processes we are developing will not only remove poisons such as arsenic and platinum from contaminated land and water courses, we are also confident that we can develop suitable biology and biorefining processes (or biofactories as we are calling them) that can tailor the shapes and sizes of the metallic nanoparticles they will make. This would give manufacturers of catalytic convertors, developers of cancer treatments and other applicable technologies exactly the right shape, size and functionality they need without subsequent refinement. We are also expecting to recover other high value materials such as fine chemicals, pharmaceuticals, anti-oxidants etc. from the crops during the same biorefining process.”

I last mentioned phyto-mining in my Sept. 26, 2012 post with regard to an international project being led by researchers at the University of York (UK).  The biorefining processes (biofactories) mentioned by Kirwan takes the idea of recovering platinum, etc. one step beyond phyto-mining recovery.

Here’s a picture of the flower (Alyssum) mentioned in the news release,

Alyssum montanum photographed by myself in 1988, Unterfranken, Germany [http://en.wikipedia.org/wiki/Alyssum]

From the Wikipedia essay (Note: I have removed links],

Alyssum is a genus of about 100–170 species of flowering plants in the family Brassicaceae, native to Europe, Asia, and northern Africa, with the highest species diversity in the Mediterranean region. The genus comprises annual and perennial herbaceous plants or (rarely) small shrubs, growing to 10–100 cm tall, with oblong-oval leaves and yellow or white flowers (pink to purple in a few species).

Get the platinum out

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They’ve been using platinum catalysts, in fuel cells and metal-air batteries, which over the last five years has ranged in cost from just under $800/oz to over $2200/oz. My March 13, 2012 posting about fuel cells noted that the use of expensive metals that are not very efficient catalysts was holding back their development and entry into the marketplace,

Advances in fuel-cell technology have been stymied by the inadequacy of metals studied as catalysts. The drawback to platinum, other than cost, is that it absorbs carbon monoxide in reactions involving fuel cells powered by organic materials like formic acid. A more recently tested metal, palladium, breaks down over time.

Now chemists at Brown University have created a triple-headed metallic nanoparticle that they say outperforms and outlasts all others at the anode end in formic-acid fuel-cell reactions.

Another group of researchers at Stanford University and other institutions is suggesting an alternative to a platinum catalyst, a multi-walled carbon nanotube. From the May 27, 2012 news release written by Mark Shwartz on EurekAlert,

Multi-walled carbon nanotubes riddled with defects and impurities on the outside could replace some of the expensive platinum catalysts used in fuel cells and metal-air batteries, according to scientists at Stanford University. Their findings are published in the May 27 online edition of the journal Nature Nanotechnology.

“Platinum is very expensive and thus impractical for large-scale commercialization,” said Hongjie Dai, a professor of chemistry at Stanford and co-author of the study. “Developing a low-cost alternative has been a major research goal for several decades.”

…

For the study, the Stanford team used multi-walled carbon nanotubes consisting of two or three concentric tubes nested together. The scientists showed that shredding the outer wall, while leaving the inner walls intact, enhances catalytic activity in nanotubes, yet does not interfere with their ability to conduct electricity.

“A typical carbon nanotube has few defects,” said Yanguang Li, a postdoctoral fellow at Stanford and lead author of the study. “But defects are actually important to promote the formation of catalytic sites and to render the nanotube very active for catalytic reactions.”

Here’s how it works, from the May 27, 2012 news release on EurekAlert,

For the study, Li and his co-workers treated multi-walled nanotubes in a chemical solution. Microscopic analysis revealed that the treatment caused the outer nanotube to partially unzip and form nanosized graphene pieces that clung to the inner nanotube, which remained mostly intact.

“We found that adding a few iron and nitrogen impurities made the outer wall very active for catalytic reactions,” Dai said. “But the inside maintained its integrity, providing a path for electrons to move around. You want the outside to be very active, but you still want to have good electrical conductivity. If you used a single-wall carbon nanotube you wouldn’t have this advantage, because the damage on the wall would degrade the electrical property.”

These are two different perspectives on the reason for why fuel cells and other batteries have not had the expected impact on the marketplace. The team at Brown University states the problem as an issue with the effectiveness of the metal catalysts where the Stanford-led team states the problem as being the cost of the metal used. Dexter Johnson in a March 9, 2012 posting on the Nanoclast blog on the IEEE (Institute of Electrical and Electronics Engineers) website suggested a third issue,

One of the fundamental problems with fuel cells has been the cost of producing hydrogen. While hydrogen is, of course, the most abundant element, it attaches itself to other elements like nitrogen or fluorine, and perhaps most ubiquitously to oxygen to create the water molecule. The process used to separate hydrogen out into hydrogen gas for powering fuel cells now relies on electricity produced from fossil fuels, negating some of the potential environmental benefits.

In his May 30, 2012 posting about this new work from Stanford, Dexter notes yet another issue impeding widespread commercialization,

… but the two main issues that have prevented fuel cells from gaining wider adoption—at least in the area of powering automobiles—are the costs of isolating hydrogen and building an infrastructure that would deliver that hydrogen to the automobiles.

Dexter mentions another application (metal-air batteries) that may benefit more from this latest work (from Dexter’s May 30, 2012 posting),

I think it’s all together possible that researchers at IBM and the US national labs who have been working on metal-air batteries for years now might be somewhat more interested in this line of research than fuel-cell manufacturers.

As one of the researchers notes (from the May 27, 2012 news release on EurekAlert),

“Lithium-air batteries are exciting because of their ultra-high theoretical energy density, which is more than 10 times higher than today’s best lithium ion technology,” Dai said. “But one of the stumbling blocks to development has been the lack of a high-performance, low-cost catalyst. Carbon nanotubes could be an excellent alternative to the platinum, palladium and other precious-metal catalysts now in use.”

The Stanford team made one other discovery as they were testing the carbon nanotubes,

The Stanford study might also have resolved a long-standing scientific controversy about the chemical structure of catalytic active sites where oxygen reactions occur. “One group of scientists believes that iron impurities are bonded to nitrogen at the active site,” Li said. “Another group believes that iron contributes virtually nothing, except to promote active sites made entirely of nitrogen.”

To address the controversy, the Stanford team enlisted scientists at Oak Ridge National Laboratory to conduct atomic-scale imaging and spectroscopy analysis of the nanotubes. The results showed clear, visual evidence of iron and nitrogen atoms in close proximity.

“For the first time, we were able to image individual atoms on this kind of catalyst,” Dai said. “All of the images showed iron and nitrogen close together, suggesting that the two elements are bonded. This kind of imaging is possible, because the graphene pieces are just one-atom thick.”

Dai noted that the iron impurities, which enhanced catalytic activity, actually came from metal seeds that were used to make the nanotubes and were not intentionally added by the scientists. The discovery of these accidental yet invaluable bits of iron offered the researchers an important lesson. “We learned that metal impurities in nanotubes must not be ignored,” Dai said.

Butterflies give and give; this time they inspire more green fuel production

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Butterflies are proving to be quite generous as they inspire ideas for greater production of green fuels in addition to everything else they’ve inspired. From the March 26, 2012 news item on Nanowerk,

“We were searching the ‘art of blackness’ for the secret of how those black wings [from black butterflies] absorb so much sunlight and reflect so little,” Fan [Tongxiang Fan, Ph.D] explained.…

Fan’s team observed elongated rectangular scales arranged like overlapping shingles on the roof of a house. The butterflies they examined had slightly different scales, but both had ridges running the length of the scale with very small holes on either side that opened up onto an underlying layer.

The steep walls of the ridges help funnel light into the holes, Fan explained. The walls absorb longer wavelengths of light while allowing shorter wavelengths to reach a membrane below the scales. Using the images of the scales, the researchers created computer models to confirm this filtering effect. The nano-hole arrays change from wave guides for short wavelengths to barriers and absorbers for longer wavelengths, which act just like a high-pass filtering layer.

The group used actual butterfly-wing structures to collect sunlight, employing them as templates to synthesize solar-collecting materials. They chose the black wings of the Asian butterfly Papilio helenus Linnaeus, or Red Helen, and transformed them to titanium dioxide by a process known as dip-calcining. Titanium dioxide is used as a catalyst to split water molecules into hydrogen and oxygen. Fan’s group paired this butterfly-wing patterned titanium dioxide with platinum nanoparticles to increase its water-splitting power. The butterfly-wing compound catalyst produced hydrogen gas from water at more than twice the rate of the unstructured compound catalyst on its own.

This work was presented at the American Chemical Society’s 243rd annual meeting themed Chemistry of Life  in San Diego, California, March 25-29, 2012.

As I’ve noted previously, although that was specific to Morpho butterflies (my Feb. 14, 2012 posting), butterflies are being very generous with their intellectual property.