Tag Archives: platinum

Are copper nanoparticles good candidates for synthesizing medicine?

This research appears to be a collaboration between Russian and Indian scientists. From a December 5, 2017 news item on Nanowerk (Note: A link has been removed),

Chemists of Ural Federal University with colleagues from India proved the effectiveness of copper nanoparticles as a catalyst on the example of analysis of 48 organic synthesis reactions (Coordination Chemistry Reviews, “Copper nanoparticles as inexpensive and efficient catalyst: A valuable contribution in organic synthesis”).

One of the advantages of the catalyst is its insolubility in traditional organic solvents. This makes copper nanoparticles a valuable alternative to heavy metal catalysts, for example palladium, which is currently used for the synthesis of many pharmaceuticals and is toxic for cells.

“Copper nanoparticles are an ideal variant of a heterophasic catalyst, since they exist in a wide variety of geometric shapes and sizes, which directly affects the surface of effective mass transfer, so reactions in the presence of this catalyst are characterized by shorter reaction times, selectivity and better yields,” says co-author Grigory Zyryanov, Doctor of Chemistry, Associate Professor of the Department of Organic and Biomolecular Chemistry of UrFU.

A December 11, 2017 (there can be a gap between distributing a press release and posting it on the home website) Ural Federal University press release, which originated the news item, makes the case for copper nanoparticles as catalytic agents,

Copper nanoparticles are inexpensive since there are many simple ways to obtain them from cheap raw materials and these methods are constantly being modified. As a result, it is possible to receive a highly porous structure of catalyst based on copper nanoparticles with a pore size of several tens to several hundred nanometers. Due to the small particle size, the area of the catalytic surface is enormous. Moreover, due to the insolubility of copper nanoparticles, the reactions catalyzed by them go on the surface of the catalyst. After the reaction is completed, the copper nanoparticles that do not interact with the solvents are easily removed, which guarantees the absence of the catalyst admixture in the composition of the final product. These catalysts are already in demand for organic synthesis by the methods of “green chemistry”. Its main principles are simplicity, cheapness, safety of production, recyclability of the catalysts.

One of the promising areas of application of the copper nanoparticle catalyst is, first of all, the creation of medical products using cross-coupling reactions. In 2010, for work in the field of palladium catalyzed cross-coupling reactions, the Nobel Prize in Chemistry was awarded to scientists from Japan and the USA: Richard Heck, Ei-ichi Negishi and Akira Suzuki. Despite worldwide recognition, palladium catalyzed cross-coupling reactions are undesirable for the synthesis of most medications due to the toxicity of palladium for living cells and the lack of methods for reliable removal of palladium traces from the final product. In addition to toxicity, the high cost of catalysts based on palladium, as well as another catalyst for pharmaceuticals, platinum, makes the use of copper nanoparticles economically and environmentally justified.

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

Copper nanoparticles as inexpensive and efficient catalyst: A valuable contribution in organic synthesis by Nisha Kant Ojha, Grigory V. Zyryanov, Adinath Majee, Valery N. Charushin, Oleg N. Chupakhin, Sougata Santra. Coordination Chemistry Reviews Volume 353, 15 December 2017, Pages 1-57 https://doi.org/10.1016/j.ccr.2017.10.004

This paper is behind a paywall.

Gold’s origin in the universe due to cosmic collision

An hypothesis for gold’s origins was first mentioned here in a May 26, 2016 posting,

The link between this research and my side project on gold nanoparticles is a bit tenuous but this work on the origins for gold and other precious metals being found in the stars is so fascinating and I’m determined to find a connection.

An artist's impression of two neutron stars colliding. (Credit: Dana Berry / Skyworks Digital, Inc.) Courtesy: Kavli Foundation

An artist’s impression of two neutron stars colliding. (Credit: Dana Berry / Skyworks Digital, Inc.) Courtesy: Kavli Foundation

From a May 19, 2016 news item on phys.org,

The origin of many of the most precious elements on the periodic table, such as gold, silver and platinum, has perplexed scientists for more than six decades. Now a recent study has an answer, evocatively conveyed in the faint starlight from a distant dwarf galaxy.

In a roundtable discussion, published today [May 19, 2016?], The Kavli Foundation spoke to two of the researchers behind the discovery about why the source of these heavy elements, collectively called “r-process” elements, has been so hard to crack.

From the Spring 2016 Kavli Foundation webpage hosting the  “Galactic ‘Gold Mine’ Explains the Origin of Nature’s Heaviest Elements” Roundtable ,

Astronomers studying a galaxy called Reticulum II have just discovered that its stars contain whopping amounts of these metals—collectively known as “r-process” elements (See “What is the R-Process?”). Of the 10 dwarf galaxies that have been similarly studied so far, only Reticulum II bears such strong chemical signatures. The finding suggests some unusual event took place billions of years ago that created ample amounts of heavy elements and then strew them throughout the galaxy’s reservoir of gas and dust. This r-process-enriched material then went on to form Reticulum II’s standout stars.

Based on the new study, from a team of researchers at the Kavli Institute at the Massachusetts Institute of Technology, the unusual event in Reticulum II was likely the collision of two, ultra-dense objects called neutron stars. Scientists have hypothesized for decades that these collisions could serve as a primary source for r-process elements, yet the idea had lacked solid observational evidence. Now armed with this information, scientists can further hope to retrace the histories of galaxies based on the contents of their stars, in effect conducting “stellar archeology.”

Researchers have confirmed the hypothesis according to an Oct. 16, 2017 news item on phys.org,

Gold’s origin in the Universe has finally been confirmed, after a gravitational wave source was seen and heard for the first time ever by an international collaboration of researchers, with astronomers at the University of Warwick playing a leading role.

Members of Warwick’s Astronomy and Astrophysics Group, Professor Andrew Levan, Dr Joe Lyman, Dr Sam Oates and Dr Danny Steeghs, led observations which captured the light of two colliding neutron stars, shortly after being detected through gravitational waves – perhaps the most eagerly anticipated phenomenon in modern astronomy.

Marina Koren’s Oct. 16, 2017 article for The Atlantic presents a richly evocative view (Note: Links have been removed),

Some 130 million years ago, in another galaxy, two neutron stars spiraled closer and closer together until they smashed into each other in spectacular fashion. The violent collision produced gravitational waves, cosmic ripples powerful enough to stretch and squeeze the fabric of the universe. There was a brief flash of light a million trillion times as bright as the sun, and then a hot cloud of radioactive debris. The afterglow hung for several days, shifting from bright blue to dull red as the ejected material cooled in the emptiness of space.

Astronomers detected the aftermath of the merger on Earth on August 17. For the first time, they could see the source of universe-warping forces Albert Einstein predicted a century ago. Unlike with black-hole collisions, they had visible proof, and it looked like a bright jewel in the night sky.

But the merger of two neutron stars is more than fireworks. It’s a factory.

Using infrared telescopes, astronomers studied the spectra—the chemical composition of cosmic objects—of the collision and found that the plume ejected by the merger contained a host of newly formed heavy chemical elements, including gold, silver, platinum, and others. Scientists estimate the amount of cosmic bling totals about 10,000 Earth-masses of heavy elements.

I’m not sure exactly what this image signifies but it did accompany Koren’s article so presumably it’s a representation of colliding neutron stars,

NSF / LIGO / Sonoma State University /A. Simonnet. Downloaded from: https://www.theatlantic.com/science/archive/2017/10/the-making-of-cosmic-bling/543030/

An Oct. 16, 2017 University of Warwick press release (also on EurekAlert), which originated the news item on phys.org, provides more detail,

Huge amounts of gold, platinum, uranium and other heavy elements were created in the collision of these compact stellar remnants, and were pumped out into the universe – unlocking the mystery of how gold on wedding rings and jewellery is originally formed.

The collision produced as much gold as the mass of the Earth. [emphasis mine]

This discovery has also confirmed conclusively that short gamma-ray bursts are directly caused by the merging of two neutron stars.

The neutron stars were very dense – as heavy as our Sun yet only 10 kilometres across – and they collided with each other 130 million years ago, when dinosaurs roamed the Earth, in a relatively old galaxy that was no longer forming many stars.

They drew towards each other over millions of light years, and revolved around each other increasingly quickly as they got closer – eventually spinning around each other five hundred times per second.

Their merging sent ripples through the fabric of space and time – and these ripples are the elusive gravitational waves spotted by the astronomers.

The gravitational waves were detected by the Advanced Laser Interferometer Gravitational-Wave Observatory (Adv-LIGO) on 17 August this year [2017], with a short duration gamma-ray burst detected by the Fermi satellite just two seconds later.

This led to a flurry of observations as night fell in Chile, with a first report of a new source from the Swope 1m telescope.

Longstanding collaborators Professor Levan and Professor Nial Tanvir (from the University of Leicester) used the facilities of the European Southern Observatory to pinpoint the source in infrared light.

Professor Levan’s team was the first one to get observations of this new source with the Hubble Space Telescope. It comes from a galaxy called NGC 4993, 130 million light years away.

Andrew Levan, Professor in the Astronomy & Astrophysics group at the University of Warwick, commented: “Once we saw the data, we realised we had caught a new kind of astrophysical object. This ushers in the era of multi-messenger astronomy, it is like being able to see and hear for the first time.”

Dr Joe Lyman, who was observing at the European Southern Observatory at the time was the first to alert the community that the source was unlike any seen before.

He commented: “The exquisite observations obtained in a few days showed we were observing a kilonova, an object whose light is powered by extreme nuclear reactions. This tells us that the heavy elements, like the gold or platinum in jewellery are the cinders, forged in the billion degree remnants of a merging neutron star.”

Dr Samantha Oates added: “This discovery has answered three questions that astronomers have been puzzling for decades: what happens when neutron stars merge? What causes the short duration gamma-ray bursts? Where are the heavy elements, like gold, made? In the space of about a week all three of these mysteries were solved.”

Dr Danny Steeghs said: “This is a new chapter in astrophysics. We hope that in the next few years we will detect many more events like this. Indeed, in Warwick we have just finished building a telescope designed to do just this job, and we expect it to pinpoint these sources in this new era of multi-messenger astronomy”.

Congratulations to all of the researchers involved in this work!

Many, many research teams were  involved. Here’s a sampling of their news releases which focus on their areas of research,

University of the Witwatersrand (South Africa)


Weizmann Institute of Science (Israel)


Carnegie Institution for Science (US)


Northwestern University (US)


National Radio Astronomy Observatory (US)


Max-Planck-Gesellschaft (Germany)


Penn State (Pennsylvania State University; US)


University of California – Davis


The American Association for the Advancement of Science’s (AAAS) magazine, Science, has published seven papers on this research. Here’s an Oct. 16, 2017 AAAS news release with an overview of the papers,


I’m sure there are more news releases out there and that there will be many more papers published in many journals, so if this interests, I encourage you to keep looking.

Two final pieces I’d like to draw your attention to: one answers basic questions and another focuses on how artists knew what to draw when neutron stars collide.

Keith A Spencer’s Oct. 18, 2017 piece on salon.com answers a lot of basic questions for those of us who don’t have a background in astronomy. Here are a couple of examples,

What is a neutron star?

Okay, you know how atoms have protons, neutrons, and electrons in them? And you know how protons are positively charged, and electrons are negatively charged, and neutrons are neutral?

Yeah, I remember that from watching Bill Nye as a kid.

Totally. Anyway, have you ever wondered why the negatively-charged electrons and the positively-charged protons don’t just merge into each other and form a neutral neutron? I mean, they’re sitting there in the atom’s nucleus pretty close to each other. Like, if you had two magnets that close, they’d stick together immediately.

I guess now that you mention it, yeah, it is weird.

Well, it’s because there’s another force deep in the atom that’s preventing them from merging.

It’s really really strong.

The only way to overcome this force is to have a huge amount of matter in a really hot, dense space — basically shove them into each other until they give up and stick together and become a neutron. This happens in very large stars that have been around for a while — the core collapses, and in the aftermath, the electrons in the star are so close to the protons, and under so much pressure, that they suddenly merge. There’s a big explosion and the outer material of the star is sloughed off.

Okay, so you’re saying under a lot of pressure and in certain conditions, some stars collapse and become big balls of neutrons?

Pretty much, yeah.

So why do the neutrons just stick around in a huge ball? Aren’t they neutral? What’s keeping them together? 

Gravity, mostly. But also the strong nuclear force, that aforementioned weird strong force. This isn’t something you’d encounter on a macroscopic scale — the strong force only really works at the type of distances typified by particles in atomic nuclei. And it’s different, fundamentally, than the electromagnetic force, which is what makes magnets attract and repel and what makes your hair stick up when you rub a balloon on it.

So these neutrons in a big ball are bound by gravity, but also sticking together by virtue of the strong nuclear force. 

So basically, the new ball of neutrons is really small, at least, compared to how heavy it is. That’s because the neutrons are all clumped together as if this neutron star is one giant atomic nucleus — which it kinda is. It’s like a giant atom made only of neutrons. If our sun were a neutron star, it would be less than 20 miles wide. It would also not be something you would ever want to get near.

Got it. That means two giant balls of neutrons that weighed like, more than our sun and were only ten-ish miles wide, suddenly smashed into each other, and in the aftermath created a black hole, and we are just now detecting it on Earth?

Exactly. Pretty weird, no?

Spencer does a good job of gradually taking you through increasingly complex explanations.

For those with artistic interests, Neel V. Patel tries to answer a question about how artists knew what draw when neutron stars collided in his Oct. 18, 2017 piece for Slate.com,

All of these things make this discovery easy to marvel at and somewhat impossible to picture. Luckily, artists have taken up the task of imagining it for us, which you’ve likely seen if you’ve already stumbled on coverage of the discovery. Two bright, furious spheres of light and gas spiraling quickly into one another, resulting in a massive swell of lit-up matter along with light and gravitational waves rippling off speedily in all directions, towards parts unknown. These illustrations aren’t just alluring interpretations of a rare phenomenon; they are, to some extent, the translation of raw data and numbers into a tangible visual that gives scientists and nonscientists alike some way of grasping what just happened. But are these visualizations realistic? Is this what it actually looked like? No one has any idea. Which is what makes the scientific illustrators’ work all the more fascinating.

“My goal is to represent what the scientists found,” says Aurore Simmonet, a scientific illustrator based at Sonoma State University in Rohnert Park, California. Even though she said she doesn’t have a rigorous science background (she certainly didn’t know what a kilonova was before being tasked to illustrate one), she also doesn’t believe that type of experience is an absolute necessity. More critical, she says, is for the artist to have an interest in the subject matter and in learning new things, as well as a capacity to speak directly to scientists about their work.

Illustrators like Simmonet usually start off work on an illustration by asking the scientist what’s the biggest takeaway a viewer should grasp when looking at a visual. Unfortunately, this latest discovery yielded a multitude of papers emphasizing different conclusions and highlights. With so many scientific angles, there’s a stark challenge in trying to cram every important thing into a single drawing.

Clearly, however, the illustrations needed to center around the kilonova. Simmonet loves colors, so she began by discussing with the researchers what kind of color scheme would work best. The smash of two neutron stars lends itself well to deep, vibrant hues. Simmonet and Robin Dienel at the Carnegie Institution for Science elected to use a wide array of colors and drew bright cracking to show pressure forming at the merging. Others, like Luis Calcada at the European Southern Observatory, limited the color scheme in favor of emphasizing the bright moment of collision and the signal waves created by the kilonova.

Animators have even more freedom to show the event, since they have much more than a single frame to play with. The Conceptual Image Lab at NASA’s [US National Aeronautics and Space Administration] Goddard Space Flight Center created a short video about the new findings, and lead animator Brian Monroe says the video he and his colleagues designed shows off the evolution of the entire process: the rising action, climax, and resolution of the kilonova event.

The illustrators try to adhere to what the likely physics of the event entailed, soliciting feedback from the scientists to make sure they’re getting it right. The swirling of gas, the direction of ejected matter upon impact, the reflection of light, the proportions of the objects—all of these things are deliberately framed such that they make scientific sense. …

Do take a look at Patel’s piece, if for no other reason than to see all of the images he has embedded there. You may recognize Aurore Simmonet’s name from the credit line in the second image I have embedded here.

Plasmonic ‘Goldfinger’: antifungal nail polish with metallic nanoparticles

A March 29,.2017 news item on Nanowerk announces a new kind of nanopolish,

Since ancient times, people have used lustrous silver, platinum and gold to make jewelry and other adornments. Researchers have now developed a new way to add the metals to nail polish with minimal additives, resulting in durable, tinted — and potentially antibacterial — nail coloring.

Using metal nanoparticles in clear nail polish makes it durable and colorful without extra additives.
Credit: American Chemical Society

A March 29, 2017 American Chemical Society (ACS) news release (also on EurekAlert), which originated the news item, adds a little more detail (Note: A link has been removed),

Nail polish comes in a bewildering array of colors. Current coloring techniques commonly incorporate pigment powders and additives. Scientists have recently started exploring the use of nanoparticles in polishes and have found that they can improve their durability and, in the case of silver nanoparticles, can treat fungal toenail infections. Marcus Lau, Friedrich Waag and Stephan Barcikowski wanted to see if they could come up with a simple way to integrate metal nanoparticles in nail polish.

The researchers started with store-bought bottles of clear, colorless nail polish and added small pieces of silver, gold, platinum or an alloy to them. To break the metals into nanoparticles, they shone a laser on them in short bursts over 15 minutes. Analysis showed that the method resulted in a variety of colored, transparent polishes with a metallic sheen. The researchers also used laser ablation to produce a master batch of metal nanoparticles in ethyl acetate, a polish thinner, which could then be added to individual bottles of polish. This could help boost the amount of production for commercialization. The researchers say the technique could also be used to create coatings for medical devices.

The authors acknowledge funding from the INTERREG-Program Germany-Netherlands.

A transparent nail varnish can be colored simply and directly with laser-generated nanoparticles. This does not only enable coloring of the varnish for cosmetic purposes, but also gives direct access to nanodoped varnishes to be used on any solid surface. Therefore, nanoparticle properties such as plasmonic properties or antibacterial effects can be easily adapted to surfaces for medical or optical purposes. The presented method for integration of metal (gold, platinum, silver, and alloy) nanoparticles into varnishes is straightforward and gives access to nanodoped polishes with optical properties, difficult to be achieved by dispersing powder pigments in the high-viscosity liquids. Courtesy: Industrial and Engineering & Chemistry Research

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

Direct Integration of Laser-Generated Nanoparticles into Transparent Nail Polish: The Plasmonic “Goldfinger” by Marcus Lau, Friedrich Waag, and Stephan Barcikowski. Ind. Eng. Chem. Res., 2017, 56 (12), pp 3291–3296 DOI: 10.1021/acs.iecr.7b00039 Publication Date (Web): March 7, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

The origins of gold and other precious metals

The link between this research and my side project on gold nanoparticles is a bit tenuous but this work on the origins for gold and other precious metals being found in the stars is so fascinating and I’m determined to find a connection.

An artist's impression of two neutron stars colliding. (Credit: Dana Berry / Skyworks Digital, Inc.) Courtesy: Kavli Foundation

An artist’s impression of two neutron stars colliding. (Credit: Dana Berry / Skyworks Digital, Inc.) Courtesy: Kavli Foundation

From a May 19, 2016 news item on phys.org,

The origin of many of the most precious elements on the periodic table, such as gold, silver and platinum, has perplexed scientists for more than six decades. Now a recent study has an answer, evocatively conveyed in the faint starlight from a distant dwarf galaxy.

In a roundtable discussion, published today [May 19, 2016?], The Kavli Foundation spoke to two of the researchers behind the discovery about why the source of these heavy elements, collectively called “r-process” elements, has been so hard to crack.

From the Spring 2016 Kavli Foundation webpage hosting the  “Galactic ‘Gold Mine’ Explains the Origin of Nature’s Heaviest Elements” Roundtable ,

RESEARCHERS HAVE SOLVED a 60-year-old mystery regarding the origin of the heaviest elements in nature, conveyed in the faint starlight from a distant dwarf galaxy.

Most of the chemical elements, composing everything from planets to paramecia, are forged by the nuclear furnaces in stars like the Sun. But the cosmic wellspring for a certain set of heavy, often valuable elements like gold, silver, lead and uranium, has long evaded scientists.

Astronomers studying a galaxy called Reticulum II have just discovered that its stars contain whopping amounts of these metals—collectively known as “r-process” elements (See “What is the R-Process?”). Of the 10 dwarf galaxies that have been similarly studied so far, only Reticulum II bears such strong chemical signatures. The finding suggests some unusual event took place billions of years ago that created ample amounts of heavy elements and then strew them throughout the galaxy’s reservoir of gas and dust. This r-process-enriched material then went on to form Reticulum II’s standout stars.

Based on the new study, from a team of researchers at the Kavli Institute at the Massachusetts Institute of Technology, the unusual event in Reticulum II was likely the collision of two, ultra-dense objects called neutron stars. Scientists have hypothesized for decades that these collisions could serve as a primary source for r-process elements, yet the idea had lacked solid observational evidence. Now armed with this information, scientists can further hope to retrace the histories of galaxies based on the contents of their stars, in effect conducting “stellar archeology.”

The Kavli Foundation recently spoke with three astrophysicists about how this discovery can unlock clues about galactic evolution as well as the abundances of certain elements on Earth we use for everything from jewelry-making to nuclear power generation. The participants were:

  • Alexander Ji – is a graduate student in physics at the Massachusetts Institute of Technology (MIT) and a member of the MIT Kavli Institute for Astrophysics and Space Research (MKI). He is lead author of a paper in Nature describing this discovery.
  • Anna Frebel – is the Silverman Family Career Development Assistant Professor in the Department of Physics at MIT and also a member of MKI. Frebel is Ji’s advisor and coauthored the Nature paper. Her work delves into the chemical and physical conditions of the early universe as conveyed by the oldest stars.
  • Enrico Ramirez-Ruiz – is a Professor of Astronomy and Astrophysics at the University of California, Santa Cruz. His research explores violent events in the universe, including the mergers of neutron stars and their role in generating r-process elements.

Here’s a link to and citation for Ji’s and Frebel’s paper about r-process elements in the stars,

R-process enrichment from a single event in an ancient dwarf galaxy by Alexander P. Ji, Anna Frebel, Anirudh Chiti, & Joshua D. Simon. Nature 531, 610–613 (31 March 2016) doi:10.1038/nature17425 Published online 21 March 2016

This paper is behind a paywall but you can read an edited transcript of the roundtable discussion on the Galactic ‘Gold Mine’ Explains the Origin of Nature’s Heaviest Elements webpage (keep scrolling past the introductory text).

As for my side project, Steep (2) on gold nanoparticles, that’s still in the planning stages but if there’s a way to include this information, I’ll do it.

South Africa, energy, and nanotechnology

South African academics Nosipho Moloto, Associate Professor, Department of Chemistry, University of the Witwatersrand and Siyabonga P. Ngubane, Lecturer in Chemistry, University of the Witwatersrand have written a Feb. 17, 2016 article for The Conversation (also available on the South African Broadcasting Corporation website) about South Africa’s energy needs and its nanotechnology efforts (Note: Links have been removed),

Energy is an economic driver of both developed and developing countries. South Africa over the past few years has faced an energy crisis with rolling blackouts between 2008 and 2015. Part of the problem has been attributed to mismanagement by the state-owned utility company Eskom, particularly the shortcomings of maintenance plans on several plants.

But South Africa has two things going for it that could help it out of its current crisis. By developing a strong nanotechnology capability and applying this to its rich mineral reserves the country is well-placed to develop new energy technologies.

Nanotechnology has already shown that it has the potential to alleviate energy problems. …

It can also yield materials with new properties and the miniaturisation of devices. For example, since the discovery of graphene, a single atomic layer of graphite, several applications in biological engineering, electronics and composite materials have been identified. These include economic and efficient devices like solar cells and lithium ion secondary batteries.

Nanotechnology has seen an incredible increase in commercialisation. Nearly 10,000 patents have been filed by large corporations since its beginning in 1991. There are already a number of nanotechnology products and solutions on the market. Examples include Miller’s beer bottling composites, Armor’s N-Force line bulletproof vests and printed solar cells produced by Nanosolar – as well as Samsung’s nanotechnology television.

The advent of nanotechnology in South Africa began with the South African Nanotechnology Initiative in 2002. This was followed by the a [sic] national nanotechnology strategy in 2003.

The government has spent more than R450 million [Rand] in nanotechnology and nanosciences research since 2006. For example, two national innovation centres have been set up and funding has been made available for equipment. There has also been flagship funding.

The country could be globally competitive in this field due to the infancy of the technology. As such, there are plenty of opportunities to make novel discoveries in South Africa.

Mineral wealth

There is another major advantage South Africa has that could help diversify its energy supply. It has an abundance of mineral wealth with an estimated value of US$2.5 trillion. The country has the world’s largest reserves of manganese and platinum group metals. It also has massive reserves of gold, diamonds, chromite ore and vanadium.

Through beneficiation and nanotechnology these resources could be used to cater for the development of new energy technologies. Research in beneficiation of minerals for energy applications is gaining momentum. For example, Anglo American and the Department of Science and Technology have embarked on a partnership to convert hydrogen into electricity.

The Council for Scientific and Industrial research also aims to develop low cost lithium ion batteries and supercapacitors using locally mined manganese and titanium ores. There is collaborative researchto use minerals like gold to synthesize nanomaterials for application in photovoltaics.

The current photovoltaic market relies on importing solar cells or panels from Europe, Asia and the US for local assembly to produce arrays. South African UV index is one of the highest in the world which reduces the lifespan of solar panels. The key to a thriving and profitable photovoltaic sector therefore lies in local production and research and development to support the sector.

It’s worth reading the article in its entirety if you’re interested in a perspective on South Africa’s energy and nanotechnology efforts.

When an atom more or less makes a big difference

As scientists continue exploring the nanoscale, it seems that finding the number of atoms in your particle makes a difference is no longer so surprising. From a Jan. 28, 2016 news item on ScienceDaily,

Combining experimental investigations and theoretical simulations, researchers have explained why platinum nanoclusters of a specific size range facilitate the hydrogenation reaction used to produce ethane from ethylene. The research offers new insights into the role of cluster shapes in catalyzing reactions at the nanoscale, and could help materials scientists optimize nanocatalysts for a broad class of other reactions.

A Jan. 28, 2016 Georgia Institute of Technology (Georgia Tech) news release (*also on EurekAlert*), which originated the news item, expands on the theme,

At the macro-scale, the conversion of ethylene has long been considered among the reactions insensitive to the structure of the catalyst used. However, by examining reactions catalyzed by platinum clusters containing between 9 and 15 atoms, researchers in Germany and the United States found that at the nanoscale, that’s no longer true. The shape of nanoscale clusters, they found, can dramatically affect reaction efficiency.

While the study investigated only platinum nanoclusters and the ethylene reaction, the fundamental principles may apply to other catalysts and reactions, demonstrating how materials at the very smallest size scales can provide different properties than the same material in bulk quantities. …

“We have re-examined the validity of a very fundamental concept on a very fundamental reaction,” said Uzi Landman, a Regents’ Professor and F.E. Callaway Chair in the School of Physics at the Georgia Institute of Technology. “We found that in the ultra-small catalyst range, on the order of a nanometer in size, old concepts don’t hold. New types of reactivity can occur because of changes in one or two atoms of a cluster at the nanoscale.”

The widely-used conversion process actually involves two separate reactions: (1) dissociation of H2 molecules into single hydrogen atoms, and (2) their addition to the ethylene, which involves conversion of a double bond into a single bond. In addition to producing ethane, the reaction can also take an alternative route that leads to the production of ethylidyne, which poisons the catalyst and prevents further reaction.

The project began with Professor Ueli Heiz and researchers in his group at the Technical University of Munich experimentally examining reaction rates for clusters containing 9, 10, 11, 12 or 13 platinum atoms that had been placed atop a magnesium oxide substrate. The 9-atom nanoclusters failed to produce a significant reaction, while larger clusters catalyzed the ethylene hydrogenation reaction with increasingly better efficiency. The best reaction occurred with 13-atom clusters.

Bokwon Yoon, a research scientist in Georgia Tech’s Center for Computational Materials Science, and Landman, the center’s director, then used large-scale first-principles quantum mechanical simulations to understand how the size of the clusters – and their shape – affected the reactivity. Using their simulations, they discovered that the 9-atom cluster resembled a symmetrical “hut,” while the larger clusters had bulges that served to concentrate electrical charges from the substrate.

“That one atom changes the whole activity of the catalyst,” Landman said. “We found that the extra atom operates like a lightning rod. The distribution of the excess charge from the substrate helps facilitate the reaction. Platinum 9 has a compact shape that doesn’t facilitate the reaction, but adding just one atom changes everything.”

Here’s an illustration featuring the difference between a 9 atom cluster and a 10 atom cluster,

A single atom makes a difference in the catalytic properties of platinum nanoclusters. Shown are platinum 9 (top) and platinum 10 (bottom). (Credit: Uzi Landman, Georgia Tech)

A single atom makes a difference in the catalytic properties of platinum nanoclusters. Shown are platinum 9 (top) and platinum 10 (bottom). (Credit: Uzi Landman, Georgia Tech)

The news release explains why the larger clusters function as catalysts,

Nanoclusters with 13 atoms provided the maximum reactivity because the additional atoms shift the structure in a phenomena Landman calls “fluxionality.” This structural adjustment has also been noted in earlier work of these two research groups, in studies of clusters of gold [emphasis mine] which are used in other catalytic reactions.

“Dynamic fluxionality is the ability of the cluster to distort its structure to accommodate the reactants to actually enhance reactivity,” he explained. “Only very small aggregates of metal can show such behavior, which mimics a biochemical enzyme.”

The simulations showed that catalyst poisoning also varies with cluster size – and temperature. The 10-atom clusters can be poisoned at room temperature, while the 13-atom clusters are poisoned only at higher temperatures, helping to account for their improved reactivity.

“Small really is different,” said Landman. “Once you get into this size regime, the old rules of structure sensitivity and structure insensitivity must be assessed for their continued validity. It’s not a question anymore of surface-to-volume ratio because everything is on the surface in these very small clusters.”

While the project examined only one reaction and one type of catalyst, the principles governing nanoscale catalysis – and the importance of re-examining traditional expectations – likely apply to a broad range of reactions catalyzed by nanoclusters at the smallest size scale. Such nanocatalysts are becoming more attractive as a means of conserving supplies of costly platinum.

“It’s a much richer world at the nanoscale than at the macroscopic scale,” added Landman. “These are very important messages for materials scientists and chemists who wish to design catalysts for new purposes, because the capabilities can be very different.”

Along with the experimental surface characterization and reactivity measurements, the first-principles theoretical simulations provide a unique practical means for examining these structural and electronic issues because the clusters are too small to be seen with sufficient resolution using most electron microscopy techniques or traditional crystallography.

“We have looked at how the number of atoms dictates the geometrical structure of the cluster catalysts on the surface and how this geometrical structure is associated with electronic properties that bring about chemical bonding characteristics that enhance the reactions,” Landman added.

I highlighted the news release’s reference to gold nanoclusters as I have noted the number issue in two April 14, 2015 postings, neither of which featured Georgia Tech, Gold atoms: sometimes they’re a metal and sometimes they’re a molecule and Nature’s patterns reflected in gold nanoparticles.

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

Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters by Andrew S. Crampton, Marian D. Rötzer, Claron J. Ridge, Florian F. Schweinberger, Ueli Heiz, Bokwon Yoon, & Uzi Landman.  Nature Communications 7, Article number: 10389  doi:10.1038/ncomms10389 Published 28 January 2016

This paper is open access.

*’also on EurekAlert’ added Jan. 29, 2016.

Hybrid bacterial genes and virus shell combined to create ‘nano reactor’ for hydrogen biofuel

Turning water into fuel may seem like an almost biblical project (e.g., Jesus turning water to wine in the New Testament) but scientists at Indiana University are hopeful they are halfway to their goal. From a Jan. 4, 2016 news item on ScienceDaily,

Scientists at Indiana University have created a highly efficient biomaterial that catalyzes the formation of hydrogen — one half of the “holy grail” of splitting H2O to make hydrogen and oxygen for fueling cheap and efficient cars that run on water.

A Jan. 4, 2016 Indiana University (IU) news release (also on EurekAlert*), which originated the news item, explains further (Note: Links have been removed),

A modified enzyme that gains strength from being protected within the protein shell — or “capsid” — of a bacterial virus, this new material is 150 times more efficient than the unaltered form of the enzyme.

“Essentially, we’ve taken a virus’s ability to self-assemble myriad genetic building blocks and incorporated a very fragile and sensitive enzyme with the remarkable property of taking in protons and spitting out hydrogen gas,” said Trevor Douglas, the Earl Blough Professor of Chemistry in the IU Bloomington College of Arts and Sciences’ Department of Chemistry, who led the study. “The end result is a virus-like particle that behaves the same as a highly sophisticated material that catalyzes the production of hydrogen.”

The genetic material used to create the enzyme, hydrogenase, is produced by two genes from the common bacteria Escherichia coli, inserted inside the protective capsid using methods previously developed by these IU scientists. The genes, hyaA and hyaB, are two genes in E. coli that encode key subunits of the hydrogenase enzyme. The capsid comes from the bacterial virus known as bacteriophage P22.

The resulting biomaterial, called “P22-Hyd,” is not only more efficient than the unaltered enzyme but also is produced through a simple fermentation process at room temperature.

The material is potentially far less expensive and more environmentally friendly to produce than other materials currently used to create fuel cells. The costly and rare metal platinum, for example, is commonly used to catalyze hydrogen as fuel in products such as high-end concept cars.

“This material is comparable to platinum, except it’s truly renewable,” Douglas said. “You don’t need to mine it; you can create it at room temperature on a massive scale using fermentation technology; it’s biodegradable. It’s a very green process to make a very high-end sustainable material.”

In addition, P22-Hyd both breaks the chemical bonds of water to create hydrogen and also works in reverse to recombine hydrogen and oxygen to generate power. “The reaction runs both ways — it can be used either as a hydrogen production catalyst or as a fuel cell catalyst,” Douglas said.

The form of hydrogenase is one of three occurring in nature: di-iron (FeFe)-, iron-only (Fe-only)- and nitrogen-iron (NiFe)-hydrogenase. The third form was selected for the new material due to its ability to easily integrate into biomaterials and tolerate exposure to oxygen.

NiFe-hydrogenase also gains significantly greater resistance upon encapsulation to breakdown from chemicals in the environment, and it retains the ability to catalyze at room temperature. Unaltered NiFe-hydrogenase, by contrast, is highly susceptible to destruction from chemicals in the environment and breaks down at temperatures above room temperature — both of which make the unprotected enzyme a poor choice for use in manufacturing and commercial products such as cars.

These sensitivities are “some of the key reasons enzymes haven’t previously lived up to their promise in technology,” Douglas said. Another is their difficulty to produce.

“No one’s ever had a way to create a large enough amount of this hydrogenase despite its incredible potential for biofuel production. But now we’ve got a method to stabilize and produce high quantities of the material — and enormous increases in efficiency,” he said.

The development is highly significant according to Seung-Wuk Lee, professor of bioengineering at the University of California-Berkeley, who was not a part of the study.

“Douglas’ group has been leading protein- or virus-based nanomaterial development for the last two decades. This is a new pioneering work to produce green and clean fuels to tackle the real-world energy problem that we face today and make an immediate impact in our life in the near future,” said Lee, whose work has been cited in a U.S. Congressional report on the use of viruses in manufacturing.

Beyond the new study, Douglas and his colleagues continue to craft P22-Hyd into an ideal ingredient for hydrogen power by investigating ways to activate a catalytic reaction with sunlight, as opposed to introducing elections using laboratory methods.

“Incorporating this material into a solar-powered system is the next step,” Douglas said.

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

Self-assembling biomolecular catalysts for hydrogen production by Paul C. Jordan, Dustin P. Patterson, Kendall N. Saboda, Ethan J. Edwards, Heini M. Miettinen, Gautam Basu, Megan C. Thielges, & Trevor Douglas. Nature Chemistry (2015) doi:10.1038/nchem.2416 Published online 21 December 2015

This paper is behind a paywall.

*(also on EurekAlert) added on Jan. 5, 2016 at 1550 PST.

Nanoscale snowman and Season’s Greetings

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

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?

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.