Tag Archives: palladium nanoparticles

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,

Hector Barron Escobar and his virtual nanomaterial atomic models for the oil, mining, and energy industries

I think there’s some machine translation at work in the Aug. 27, 2015 news item about Hector Barron Escobar on Azonano,

By using supercomputers the team creates virtual atomic models that interact under different conditions before being taken to the real world, allowing savings in time and money.

With the goal of potentiate the oil, mining and energy industries, as well as counteract the emission of greenhouse gases, the nanotechnologist Hector Barron Escobar, designs more efficient and profitable nanomaterials.

The Mexican who lives in Australia studies the physical and chemical properties of platinum and palladium, metal with excellent catalytic properties that improve processes in petrochemistry, solar cells and fuel cells, which because of their scarcity have a high and unprofitable price, hence the need to analyze their properties and make them long lasting.

Structured materials that the specialist in nanotechnology designs can be implemented in the petrochemical and automotive industries. In the first, they accelerate reactions in the production of hydrocarbons, and in the second, nanomaterials are placed in catalytic converters of vehicles to transform the pollutants emitted by combustion into less harmful waste.

An August 26, 2015 Investigación y Desarrollo press release on Alpha Galileo, which originated the news item, continues Barron Escobar’s profile,

PhD Barron Escobar, who majored in physics at the National University of Mexico (UNAM), says that this are created by using virtual supercomputers to interact with atomic models under different conditions before being taken to the real world.

Barron recounts how he came to Australia with an invitation of his doctoral advisor, Amanda Partner with whom he analyzed the electronic properties of gold in the United States.

He explains that using computer models in the Virtual Nanoscience Laboratory (VNLab) in Australia, he creates nanoparticles that interact in different environmental conditions such as temperature and pressure. He also analyzes their mechanical and electronic properties, which provide specific information about behavior and gives the best working conditions. Together, these data serve to establish appropriate patterns or trends in a particular application.

The work of the research team serves as a guide for experts from the University of New South Wales in Australia, with which they cooperate, to build nanoparticles with specific functions. “This way we perform virtual experiments, saving time, money and offer the type of material conditions and ideal size for a specific catalytic reaction, which by the traditional way would cost a lot of money trying to find what is the right substance” Barron Escobar comments.

Currently he designs nanomaterials for the mining company Orica, because in this industry explosives need to be controlled in order to avoid damaging the minerals or the environment.

Research is also immersed in the creation of fuel cells, with the use of the catalysts designed by Barron is possible to produce more electricity without polluting.

Additionally, they enhance the effectiveness of catalytic converters in petrochemistry, where these materials help accelerate oxidation processes of hydrogen and carbon, which are present in all chemical reactions when fuel and gasoline are created. “We can identify the ideal particles for improving this type of reactions.”

The nanotechnology specialist also seeks to analyze the catalytic properties of bimetallic materials like titanium, ruthenium and gold, as their reaction according to size, shape and its components.

Escobar Barron chose to study nanomaterials because it is interesting to see how matter at the nano level completely changes its properties: at large scale it has a definite color, but keep another at a nanoscale, besides many applications can be obtained with these metals.

For anyone interested in Orica, there’s more here on their website; as for Dr. Hector Barron Escobar, there’s this webpage on  Australia’s Commonwealth Scientific and Industrial Research Organisation (CSIRO) website.

Policing, detecting, and arresting pollution

The title for a May 13, 2015 news item on ScienceDaily was certainly eye-catching,

Nano-policing pollution

Pollutants emitted by factories and car exhausts affect humans who breathe in these harmful gases and also aggravate climate change up in the atmosphere. Being able to detect such emissions is a critically needed measure.

New research by the Nanoparticles by Design Unit at the Okinawa Institute of Science and Technology Graduate University (OIST), in collaboration with the Materials Center Leoben Austria and the Austrian Centre for Electron Microscopy and Nanoanalysis has developed an efficient way to improve methods for detecting polluting emissions using a sensor at the nanoscale. …

A May 13, 2015 OIST press release (also on EurekAlert) by Joykrit Mitra, which originated the news item, details the research (Note: A link has been removed),

The researchers used a copper oxide nanowire decorated with palladium nanoparticles to detect carbon monoxide, a common industrial pollutant.  The sensor was tested in conditions similar to ambient air since future devices developed from this method will need to operate in these conditions.

Copper oxide is a semiconductor and scientists use nanowires fabricated from it to search for potential application in the microelectronics industry. But in gas sensing applications, copper oxide was much less widely investigated compared to other metal oxide materials.

A semiconductor can be made to experience dramatic changes in its electrical properties when a small amount of foreign atoms are made to attach to its surface at high temperatures.  In this case, the copper oxide nanowire was made part of an electric circuit. The researchers detected carbon monoxide indirectly, by measuring the change in the resulting circuit’s electrical resistance in presence of the gas. They found that copper oxide nanowires decorated with palladium nanoparticles show a significantly greater increase in electrical resistance in the presence of carbon monoxide than the same type of nanowires without the nanoparticles.

The OIST Nanoparticles by Design Unit used a sophisticated technique that allowed them to first sift nanoparticles according to size, then deliver and deposit the palladium nanoparticles onto the surface of the nanowires in an evenly distributed manner. This even dispersion of size selected nanoparticles and the resulting nanoparticles-nanowire interactions are crucial to get an enhanced electrical response.  The OIST nanoparticle deposition system can be tailored to deposit multiple types of nanoparticles at the same time, segregated on distinct areas of the wafer where the nanowire sits. In other words, this system can be engineered to be able to detect multiple kinds of gases.  The next step is to detect different gases at the same time by using multiple sensor devices, with each device utilizing a different type of nanoparticle.

Compared to other options being explored in gas sensing which are bulky and difficult to miniaturize, nanowire gas sensors will be cheaper and potentially easier to mass produce.

The main energy cost in operating this kind of a sensor will be the high temperatures necessary to facilitate the chemical reactions for ensuring certain electrical response. In this study 350 degree centigrade was used.  However, different nanowire-nanoparticle material configurations are currently being investigated in order to lower the operating temperature of this system.

“I think nanoparticle-decorated nanowires have a huge potential for practical applications as it is possible to incorporate this type of technology into industrial devices,” said Stephan Steinhauer, a Japan Society for the Promotion of Science (JSPS) postdoctoral research fellow working under the supervision of Prof. Mukhles Sowwan at the OIST Nanoparticles by Design Unit.

The researchers have provided this image showing their work,

Palladium nanoparticles were deposited on the entire wafer in an evenly distributed fashion, as seen in the background.  They also attached on the surface of the copper oxide wire in the same evenly distributed manner, as seen in the foreground.   On the upper right is a top view of a single palladium nanoparticle photographed with a transmission electron microscope(TEM) which can only produce black and white images. The nanoparticle is made up of columns consisting of palladium atoms stacked on top of each other.  Courtesy OIST

Palladium nanoparticles were deposited on the entire wafer in an evenly distributed fashion, as seen in the background. They also attached on the surface of the copper oxide wire in the same evenly distributed manner, as seen in the foreground.
On the upper right is a top view of a single palladium nanoparticle photographed with a transmission electron microscope(TEM) which can only produce black and white images. The nanoparticle is made up of columns consisting of palladium atoms stacked on top of each other. Courtesy OIST

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

Single CuO nanowires decorated with size-selected Pd nanoparticles for CO sensing in humid atmosphere by Stephan Steinhauer, Vidyadhar Singh, Cathal Cassidy, Christian Gspan, Werner Grogger, Mukhles Sowwan, and Anton Köck. Nanotechnology 2015 Volume 26 Number 17 doi:10.1088/0957-4484/26/17/175502

This paper is behind a paywall.

Cleaning water with palladium nanoparticle catalysts

A Jan. 16, 2015 news item on Nanowerk describes research into using palladium as a catalyst for water remediation efforts,

One way of removing harmful nitrate from drinking water is to catalyse its conversion to nitrogen. This process suffers from the drawback that it often produces ammonia. By using palladium nanoparticles as a catalyst, and by carefully controlling their size, this drawback can be partially eliminated. It was research conducted by Yingnan Zhao of the University of Twente’s MESA+ Institute for Nanotechnology that led to this discovery.

A Jan. 14, 2015 University of Twente press release, which originated the news item, describes the problem and suggested solution; this was research for a PhD thesis,

Due to the excessive use of fertilizers, our groundwater is contaminated with nitrates, which pose a problem if they enter the mains water supply. Levels have fallen significantly in recent years, as a result of various European directives. In addition, the Integrated Approach to Nitrogen programme was launched in various Dutch nature reserves at the start of January. Tackling the problem at source is one thing, but it will still be necessary to treat the mains water supply. While this can be achieved through biological conversion – bacteria convert the nitrate to nitrogen gas-, this is a slow process. Using palladium to catalyse the conversion of nitrate to nitrogen speeds up the process enormously. However, this reaction suffers from the drawback that it produces a harmful by-product – ammonia.

Exposed surface

The amount of ammonia produced appears to depend on the method used to prepare the palladium and on the catalyst’s physical structure. Yingnan Zhao decided to use nanometre-sized colloidal palladium particles, as their dimensions can be easily controlled. These particles are fixed to a surface, so they do not end up in the mains water supply. However, it is important to stop them clumping together, so stabilizers such as polyvinyl alcohol are added. Unfortunately, these stabilizers tend to shield the surface of the palladium particles, which reduces their effectiveness as a catalyst. By introducing additional treatments, Yingnan Zhao has managed to fully expose the catalytic surface once again or to manipulate it in a controlled manner. This has resulted in palladium nanoparticles that can catalyse the conversion to nitrogen, while producing very little ammonia. This has brought the further development of catalytic water treatment (in compact devices for home use, for example) one step closer.

Yingnan Zhao, who is from Heze, Shandong, China, conducted his research in Prof. Leon Lefferts’ Catalytic Processes and Materials group. He defended his thesis, which is entitled “Colloidal Nanoparticles as Catalysts and Catalyst Precursors for Nitrite Hydrogenation” on Thursday 15 January [2015].

I trust Zhao successfully defended this thesis and perhaps more importantly helped to develop a new and better method for water remediation made necessary by the effects of fertilizers.

Animating nanoparticles

It’s always good to find new tools for explaining/describing the nanoscale and this July 28, 2014 news item on Nanowerk, which highlights animation that simulates interactions between nanoparticles, helps to fill the bill,

Panagiotis Grammatikopoulos in the OIST [Okinawa Institute of Science and Technology] Nanoparticles by Design Unit simulates the interactions of particles that are too small to see, and too complicated to visualize. In order to study the particles’ behavior, he uses a technique called molecular dynamics. This means that every trillionth of a second, he calculates the location of each individual atom in the particle based on where it is and which forces apply. He uses a computer program to make the calculations, and then animates the motion of the atoms using visualization software. The resulting animation illuminates what happens, atom-by-atom, when two nanoparticles collide.

A July 25, 2014 OIST news release by Poncie Rutsch, which originated the news item, details the process Grammatikopoulos follows, (Note: A link has been removed)

Grammatikopoulos calls this a virtual experiment. He knows what the atoms in his starting nanoparticles look like. He knows their motion follows the laws of Newtonian physics. His colleagues have seen what the resulting particles look like after collision experiments.  Once his simulation is complete, Grammatikopoulos compares his end products with his colleagues to check his accuracy.

Grammatikopoulos most recently simulated how palladium nanoparticles interact, published in Scientific Reports on July 22, 2014. Palladium is an expensive but highly efficient catalyst that lowers the energy required to start many chemical reactions. Researchers can make palladium even more efficient by designing palladium nanoparticles, which use the same mass of palladium in tinier pieces, increasing surface area. The more surface area a catalyst has, the more effective it is, because there are more active sites where elements can meet and reactions can occur.

However, shrinking a material to only a few nanometers can change some of the properties of that material. For example, all nanoparticles melt at cooler temperatures than they would normally, which changes what happens when two particles collide. Ordinarily, two particles will collide and release a small amount of heat, but the particles remain more or less the same. But when two nanoparticles collide, sometimes the heat released melts the surface of the two particles, and they fuse together.

Grammatikopoulos simulated palladium nanoparticles colliding and fusing at different temperatures. He determined that each time the particles fused, their atoms would start to crystallize into orderly rows and planes. At higher temperatures, the particles fuse into one homogeneous structure. At lower temperatures, the products look like classic snowmen, with a few parts that had crystallized with different orientations.

“The simulation gives you an understanding of physical processes,” said Grammatikopoulos. Before his research, Grammatikopoulos could not explain why all the palladium nanoparticles his lab created had a crystalline structure. Furthermore, he noticed that many palladium nanoparticles grew protrusions, giving the particles a lumpy shape. “Since the protrusions stick out, they bond more easily with other molecules,” Grammatikopoulos explained. “I’m not sure yet if it’s beneficial, but it’s definitely affecting the catalytic properties.”

Here’s an image illustrating the process,

Grammatikopoulos simulated two palladium nanoparticles colliding at different temperatures. The hotter the temperature, the more homogenous the resulting product, and the further the atoms in the particle crystallize. Courtesy: OIST

The news release goes on to explain the impact this information could have,

This study establishes some ground rules and explains certain properties of palladium nanoparticles. Understanding these properties could help design other nanoparticles out of other materials that would rival palladium’s abilities as a catalyst.  Palladium plays a role in thousands of important reactions, from making drugs to creating new biofuels. For example, Prof. Mukhles Sowwan’s Nanoparticles by Design Unit and Prof. Igor Goryanin’s Biological Systems Unit at OIST are working with palladium-catalyzed reactions to improve the efficiency of microbial fuel cells. Better palladium nanoparticles will propel this research forward.

“We need to understand the basic science,” explained Sowwan, who is Grammatikopoulos’ advisor. Sowwan says that the field of nanoscience is only starting to move towards applying the research, because there is still so much to learn about the properties of nanoparticles. “If you build something without understanding the basics,” Sowwan said, “you will not be able to explain the results.”

The researchers have made videos available, here’s a video of palladium crystallization at 300K,

As per the information provided by OIST,

Published on Jul 24, 2014

Grammatikopoulos created this simulation of palladium nanoparticles colliding at 300 Kelvin, or about 27 degrees Celsius. The nanoparticles meet, then fuse, then crystallize in orderly planes.

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

Coalescence-induced crystallisation wave in Pd nanoparticles by Panagiotis Grammatikopoulos, Cathal Cassidy, Vidyadhar Singh, & Mukhles Sowwan. Scientific Reports 4, Article number: 5779 doi:10.1038/srep05779 Published 22 July 2014

This is an  open access paper.