Tag Archives: ethylene

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.

Fruits,vegetables and flowers go deluxe with platinum nanoparticle catalyst

Before getting to the role platinum nanoparticles could play, here’s some information about ripening fruits, vegetables, and flowers, from a May 13, 2013 news item on Nanowerk,

Ripening fruit, vegetables, and flowers release ethylene, which works as a plant hormone. Ethylene accelerates ripening, so other unripened fruit also begins to ripen—fruit and vegetables quickly spoil and flowers wilt.

The news item goes on to describe a new system which could lower or eliminate rapid degradation from ethylene (Note: A link has been removed),

In the journal Angewandte Chemie (“Low-Temperature Oxidation of Ethylene over Platinum Nanoparticles Supported on Mesoporous Silica”), Japanese researchers have now introduced a new catalytic system for the fast and complete degradation of ethylene. This system could keep the air in warehouses ethylene-free, keeping perishable products fresh longer.

The May 13, 2013 article on Wiley’s (Angewandte Chemie publisher) Chemistry Views website, which originated the news item, offers more technical detail about the new system,

Atsushi Fukuoka and his co-workers at Hokkaido University tested different metals in combination with a variety of support materials to develop an effective catalyst. They met with success: Platinum nanoparticles on a support made of special mesoporous silicon dioxide (MCM-41) demonstrated very high activity in the oxidation of ethylene at 0 to 20 °C. At an ethylene concentration of 50 ppm, over 99.8 % conversion was obtained at 0 °C, a previously unattained level that remains steady over longer periods and after multiple uses.

The catalyst is made by stirring the support with an aqueous solution of a platinum salt for 18 hours. The support is then dried and heated first under oxygen and then under hydrogen. After this process, the large pores of the silicon dioxide material contain platinum particles with a size of about 2.4 nm. This particle size, as well as the effect of the silica, seem to be particularly favorable for the reaction.

It is proposed that ethylene (C2H4) and oxygen initially react rapidly on this catalyst to form formaldehyde (HCHO), which is adsorbed onto the platinum and then primarily degraded to carbon monoxide (CO) and hydrogen species that in turn react with oxygen species to make carbon dioxide and water. A small amount of formic acid is formed as a byproduct. The especially high activity of the catalyst results from the facile oxidation of CO to CO2 that occurs at platinum on silicon dioxide supports. The precise details of the reaction mechanism are currently under investigation.

For those who are interested, here are two links to (more or less, there”s more clicking ahead) and a citation for the researchers’ paper,

I believe this paper is behind a paywall.

There is at least one other nanotechnology project devoted to reducing/eliminating food wastage as I noted in my India, Sri Lanka, and Canada team up for nanotechnology-enabled food packaging posting of June 21, 2012. I did get a bit more information about this project (Prof. Jayasankar Subramanian’s at Canada’s University of Guelph is one of the principal investigators) and included it in my Nov. 1, 2012 posting.

Soldiers sniff overripe fruit

Technically speaking the soldiers are not sniffing the fruit, it’s the sensing technology developed at the Massachusetts Institute of Technology’s Institute for Soldier Nanotechnologies which is doing the ‘sniffing’. From the April 30, 2012 news item on Nanowerk (I have removed some links),

Every year, U.S. supermarkets lose roughly 10 percent of their fruits and vegetables to spoilage, according to the Department of Agriculture. To help combat those losses, MIT chemistry professor Timothy Swager and his students have built a new sensor that could help grocers and food distributors better monitor their produce.

The new sensors, described in the journal Angewandte Chemie (“Selective Detection of Ethylene Gas Using Carbon Nanotube-based Devices: Utility in Determination of Fruit Ripeness”), can detect tiny amounts of ethylene, a gas that promotes ripening in plants. Swager envisions the inexpensive sensors attached to cardboard boxes of produce and scanned with a handheld device that would reveal the contents’ ripeness.

Detecting gases to monitor the food supply is a new area of interest for Swager, whose previous research has focused on sensors to detect explosives or chemical and biological warfare agents.

Here’s how the technology works (from the April 30, 2012 news release by Anne Trafton for MIT News),

Funded by the U.S. Army Office of Research through MIT’s Institute for Soldier Nanotechnologies, the MIT team built a sensor consisting of an array of tens of thousands of carbon nanotubes: sheets of carbon atoms rolled into cylinders that act as “superhighways” for electron flow.

To modify the tubes to detect ethylene gas, the researchers added copper atoms, which serve as “speed bumps” to slow the flowing electrons. “Anytime you put something on these nanotubes, you’re making speed bumps, because you’re taking this perfect, pristine system and you’re putting something on it,” Swager says.

Copper atoms slow the electrons a little bit, but when ethylene is present, it binds to the copper atoms and slows the electrons even more. By measuring how much the electrons slow down — a property also known as resistance — the researchers can determine how much ethylene is present.

To make the device even more sensitive, the researchers added tiny beads of polystyrene, which absorbs ethylene and concentrates it near the carbon nanotubes. With their latest version, the researchers can detect concentrations of ethylene as low as 0.5 parts per million. The concentration required for fruit ripening is usually between 0.1 and one part per million.

The researchers tested their sensors on several types of fruit — banana, avocado, apple, pear and orange — and were able to accurately measure their ripeness by detecting how much ethylene the fruits secreted.

It looks like the technology will be commercialized in the not too distant future (from the Trafton news release) here’s why,

John Saffell, the technical director at Alphasense, a company that develops sensors, describes the MIT team’s approach as rigorous and focused. “This sensor, if designed and implemented correctly, could significantly reduce the level of fruit spoilage during shipping,” he says.

“At any given time, there are thousands of cargo containers on the seas, transporting fruit and hoping that they arrive at their destination with the correct degree of ripeness,” adds Saffell, who was not involved in this research. “Expensive analytical systems can monitor ethylene generation, but in the cost-sensitive shipping business, they are not economically viable for most of shipped fruit.”

Swager has filed for a patent on the technology and hopes to start a company to commercialize the sensors. In future work, he plans to add a radio-frequency identification (RFID) chip to the sensor so it can communicate wirelessly with a handheld device that would display ethylene levels. The system would be extremely cheap — about 25 cents for the carbon nanotube sensor plus another 75 cents for the RFID chip, Swager estimates.

“This could be done with absolutely dirt-cheap electronics, with almost no power,” he says.

I should mention that a couple of students were part of the MIT research team with Birgit Esser being the lead author and Jan Schnorr also contributing to the paper in Angewandte Chemie.