Tag Archives: catalysis

Seaweed supercapacitors

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

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

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

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

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

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

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

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

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

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

Here’s an image representing the research,

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

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

Discovering why nanoscale gold has catalytic properties

Gold’s glitter may have inspired poets and triggered wars, but its catalytic prowess has helped make chemical reactions greener and more efficient. (Image courtesy of iStock/sbayram) [downloaded from http://www1.lehigh.edu/news/scientists-uncover-secret-gold%E2%80%99s-catalytic-powers

Gold’s glitter may have inspired poets and triggered wars, but its catalytic prowess has helped make chemical reactions greener and more efficient. (Image courtesy of iStock/sbayram) [downloaded from http://www1.lehigh.edu/news/scientists-uncover-secret-gold%E2%80%99s-catalytic-powers

A Sept. 27, 2016 news item on phys.org describes a discovery made by scientists at Lehigh University (US),

Settling a decades-long debate, new research conclusively shows that a hierarchy of active species exists in gold on iron oxide catalysis designed for low temperature carbon monoxide oxidation; Nanoparticles, sub-nanometer clusters and dispersed atoms—as well as how the material is prepared—are all important for determining catalytic activity.

A Sept. 27, 2016 Lehigh University news release by Lori Friedman, which originated the news item, provides more information about the discovery that gold nanoparticles can be used in catalysis and about the discovery of why that’s possible,

Christopher J. Kiely calls the 1982 discovery by Masatake Haruta that gold (Au) possessed a high level of catalytic activity for carbon monoxide (CO) oxidation when deposited on a metal-oxide “a remarkable turn of events in nanotechnology”—remarkable because gold had long been assumed to be inert for catalysis.

Haruta showed that gold dispersed on iron oxide effectively catalyzed the conversion of harmful carbon monoxide into more benign carbon dioxide (CO2) at room temperatures—a reaction that is critical for the construction of fire fighters’ breathing masks and for removal of CO from hydrogen feeds for fuel cells. In fact, today gold catalysts are being exploited in a major way for the greening of many important reactions in the chemical industry, because they can lead to cleaner, more efficient reactions with fewer by-products.

Haruta and Graham J. Hutchings, who co-discovered the use of gold as a catalyst for different reactions, are noted as Thompson Reuters Citation Laureates and appear annually on the ScienceWatch Nobel Prize prediction list. Their pioneering work opened up a new area of scientific inquiry and kicked off a decades-long debate about which type of supported gold species are most effective for the CO oxidation reaction.

In 2008, using electron microscopy technology that was not yet available in the 1980s and ’90 s, Hutchings, the director of the Cardiff Catalysis Institute at Cardiff University worked with Kiely, the Harold B. Chambers Senior Professor Materials Science and Engineering at Lehigh, examined the structure of supported gold at the nanoscale. One nanometer (nm) is equal to one one-billionth of a meter or about the diameter of five atoms.

Using what was then a rare piece of equipment—Lehigh’s aberration-corrected JEOL 2200 FS scanning transmission electron microscope (STEM)—the team identified the co-existence of three distinct gold species: facetted nanoparticles larger than one nanometer in size, sub-clusters containing less than 20 atoms and individual gold atoms strewn over the support. Because only the larger gold nanoparticles had previously been detected, this created debate as to which of these species were responsible for the good catalytic behavior.

Haruta, professor of applied chemistry at Tokyo Metropolitan University, Hutchings and Kiely have been working collaboratively on this problem over recent years and are now the first to demonstrate conclusively that it is not the particles or the individual atoms or the clusters which are solely responsible for the catalysis—but that they all contribute to different degrees. Their results have been published in an article in Nature Communications titled: “Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation.”

“All of the species tend to co-exist in conventionally prepared catalysts and show some level of activity,” says Kiely. “They all do something—but some less efficiently than others.”

Their research revealed the sub-nanometer clusters and 1-3nm nanoparticles to be the most efficient for catalyzing this CO oxidation reaction, while larger particles were less so and the atoms even less.  Nevertheless, Kiely cautions, all the species present need to be considered to fully explain the overall measured activity of the catalyst.

Among the team’s other key findings: the measured activity of gold on iron oxide catalysts is exquisitely dependent on exactly how the material is prepared. Very small changes in synthesis parameters  influence the relative proportion and spatial distribution of these various Au species on the support material and thus have a big impact on its overall catalytic performance.

A golden opportunity

Building on their earlier work (published in a 2008 Science article), the team sought to find a robust way to quantitatively analyze the relative population distributions of nanoparticles of various sizes, sub-nm clusters and highly dispersed atoms in a given gold on iron oxide sample. By correlating this information with catalytic performance measurements, they then hoped to determine which species distribution would be optimal to produce the most efficient catalyst, in order to utilize the precious gold component in the most cost effective way.

Ultimately, it was a catalyst synthesis problem the team faced that offered them a golden opportunity to do just that.

During the collaboration, Haruta’s and Hutchings’ teams each prepared gold on iron oxide samples in their home labs in Tokyo and Cardiff. Even though both groups nominally utilized the same ‘co-precipitation’ synthesis method, it turned out that a final heat treatment step was beneficial to the catalytic performance for one set of materials but detrimental to the other. This observation provided a fascinating scientific conundrum that detailed electron microscopy studies performed by Qian He, one of Kiely’s PhD students at the time, was key to solving. Qian He is now a University Research Fellow at Cardiff University leading their electron microscopy effort.

“In the end, there were subtle differences in the order and speed in which each group added in their ingredients while preparing the material,” explains He. “When examined under the electron microscope, it was clear that the two slightly different methods produced quite different distributions of particles, clusters and dispersed atoms on the support.”

“Very small variations in the preparation route or thermal history of the sample can alter the relative balance of supported gold nanoparticles-to-clusters-to-atoms in the material and this manifests itself in the measured catalytic activity,” adds Kiely.

The group was able to compare this set of materials and correlate the Au species distributions with catalytic performance measurements, ultimately identifying the species distribution that was associated with greater catalytic efficiency.

Now that the team has identified the catalytic activity hierarchy associated with these supported gold species, the next step, says Kiely, will be to modify the synthesis method to positively influence that distribution to optimize the catalyst performance while making the most efficient use of the precious gold metal content.

“As a next stage to this study we would like to be able to observe gold on iron oxide materials in-situ within the electron microscope while the reaction is happening,” says Kiely.

Once again, it is next generation microscopy facilities that may hold the key to fulfilling gold’s promise as a pivotal player in green technology.

Despite the link to the paper already in the news release, here’s one that includes a citation,

Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation by Andrew A. Herzing, Christopher J. Kiely, Albert F. Carley, Philip Landon, Graham J. Hutchings. Science  05 Sep 2008: Vol. 321, Issue 5894, pp. 1331-1335 DOI: 10.1126/science.1159639

This paper is currently behind a paywall but, if you can wait one year, free access can be gained if you register (for free) with Science.

Producing catalytically active gold nanoparticles at absolute zero

A Sept. 8, 2016 news item on Nanowerk describes research into producing remarkably stable gold nanoparticles with catalytic capabilities (Note: A link has been removed),

An ultra-high-vacuum chamber with temperatures approaching absolute zero—the coldest anything can get—may be the last place you would expect to find gold. But a group of researchers from Stony Brook University (SBU) in collaboration with scientists at the Air Force Research Lab (AFRL) and the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory have just demonstrated that such a desolate place is ideal for producing catalytically active gold nanoparticles.

A paper describing the first catalyst ever produced using their new method, called Helium Nanodroplet Deposition (HND), was recently published in the Journal of Physical Chemistry Letters (“Development of a New Generation of Stable, Tunable, and Catalytically Active Nanoparticles Produced by the Helium Nanodroplet Deposition Method”).

A Sept. 7, 2016 Brookhaven National Laboratory news release by Alexander Orlov and Karen McNulty Walsh, which originated the news item, describes the work in more detail,

As lead researcher Alexander Orlov of SBU explains, HND works by boiling gold atoms in a vacuum to produce a vapor. The vaporized gold is then “picked up” by an extremely cold jet stream of liquid helium droplets that act to literally strike gold clusters against a solid collector downstream. Upon striking the collector, the liquid helium droplets instantly evaporate releasing helium gas and leaving behind unprecedentedly pure and stable gold nanoparticles.

“This new method to produce active nanoparticles offers unique opportunities to create materials with unprecedented properties to solve energy and environmental problems,” Orlov said.  “Our Brookhaven and AFRL collaborators made it possible for our students to access the most unique facilities in the world, which made all the difference in our research.”

Qiyuan Wu, a graduate student working in Orlov’s laboratory and first author on the paper, performed much of the work to develop the method. Michael Lindsay and Claron Ridge of AFRL provided state-of-the-art facilities at Eglin Air Force Base, one of only a few places in the world with the capabilities required to generate the gold nanoparticles using the new technique. And a team at the Center for Functional Nanomaterials (CFN), a DOE Office of Science User Facility at Brookhaven Lab, used advanced imaging and characterization tools to study the nanoparticles’ catalytic activity.

Specifically, Brookhaven scientists Eric Stach and Dmitri Zakharov of the CFN and Shen Zhao, then a postdoctoral fellow working under Stach, developed a method to deposit the gold nanoparticles onto a “catalyst support” structure they use for characterizing the stability of other nanomaterials. They then studied the characteristics of the nanoparticles, including their stability under reaction conditions, using the Titan Environmental Transmission Electron Microscope at the CFN. Further characterization by Zhao and CFN staff member Dong Su using aberration-corrected Scanning Transmission Electron Microscopy allowed the SBU researchers to understand how the droplets form.

“This was part of a User project, that morphed into a collaboration,” said Stach, who leads the electron microscopy group at CFN. “It was a very nice study”—and an example of how the Office of Science User Facilities offer not just unique scientific equipment but also scientific expertise that can be essential to the success of a research project.

Nanoparticles are of high research interest due to their improved properties compared to bulk materials. They have revolutionized technologies aimed at improving sustainability such as fuel cells, photocatalysts, and solar panels. The gold nanoparticle catalysts produced in this study are capable of converting poisonous carbon monoxide gas into carbon dioxide gas, an essential reaction that occurs in the catalytic converters of cars to reduce pollution and lower impacts on the environment.

According to Orlov, the HND method is not limited to the production of gold nanoparticles, but can be applied to nearly all metals and can even produce challenging multi-metallic nanoparticles. The technique’s versatility and ability to produce clean and well-defined samples make it a powerful tool for the discovery of new catalysts and studying factors that affect catalyst performance.

The collaboration is currently researching how the parameters of HND can be adjusted to control catalyst performance.

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

Development of a New Generation of Stable, Tunable, and Catalytically Active Nanoparticles Produced by the Helium Nanodroplet Deposition Method by Qiyuan Wu, Claron J. Ridge, Shen Zhao, Dmitri Zakharov, Jiajie Cen, Xiao Tong, Eoghan Connors, Dong Su, Eric A. Stach, C. Michael Lindsay, and Alexander Orlov. J. Phys. Chem. Lett., 2016, 7 (15), pp 2910–2914 DOI: 10.1021/acs.jpclett.6b01305 Publication Date (Web): July 13, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

Self-healing diamond-like carbon from the Argonne Lab (US)

Argonne researchers, from left, Subramanian Sankaranarayanan, Badri Narayanan, Ali Erdemir, Giovanni Ramirez and Osman Levent Eryilmaz show off metal engine parts that have been treated with a diamond-like carbon coating similar to one developed and explored by the team. The catalytic coating interacts with engine oil to create a self-healing diamond-like film that could have profound implications for the efficiency and durability of future engines. (photo by Wes Agresta)

Argonne researchers, from left, Subramanian Sankaranarayanan, Badri Narayanan, Ali Erdemir, Giovanni Ramirez and Osman Levent Eryilmaz show off metal engine parts that have been treated with a diamond-like carbon coating similar to one developed and explored by the team. The catalytic coating interacts with engine oil to create a self-healing diamond-like film that could have profound implications for the efficiency and durability of future engines. (photo by Wes Agresta)

An Aug. 5, 2016 news item on ScienceDaily makes the announcement,

Fans of Superman surely recall how the Man of Steel used immense heat and pressure generated by his bare hands to form a diamond out of a lump of coal.

The tribologists — scientists who study friction, wear, and lubrication — and computational materials scientists at the U.S. Department of Energy’s (DOE’s) Argonne National Laboratory will probably never be mistaken for superheroes. However, they recently applied the same principles and discovered a revolutionary diamond-like film of their own that is generated by the heat and pressure of an automotive engine.

An Aug. 5, 2016 Argonne National Laboratory news release (also on EurekAlert) by Greg Cunningham, which originated the news item, explains further,

The discovery of this ultra-durable, self-lubricating tribofilm – a film that forms between moving surfaces — was first reported yesterday in the journal Nature. It could have profound implications for the efficiency and durability of future engines and other moving metal parts that can be made to develop self-healing, diamond-like carbon (DLC) tribofilms.

“This is a very unique discovery, and one that was a little unexpected,” said Ali Erdemir, the Argonne Distinguished Fellow who leads the team. “We have developed many types of diamond-like carbon coatings of our own, but we’ve never found one that generates itself by breaking down the molecules of the lubricating oil and can actually regenerate the tribofilm as it is worn away.”

The phenomenon was first discovered several years ago by Erdemir and his colleague Osman Levent Eryilmaz in the Tribology and Thermal-Mechanics Department in Argonne’s Center for Transportation Research. But it took theoretical insight enhanced by the massive computing resources available at Argonne to fully understand what was happening at the molecular level in the experiments. The theoretical understanding was provided by lead theoretical researcher Subramanian Sankaranarayanan and postdoctoral researcher Badri Narayanan from the Center for Nanoscale Materials (CNM), while the computing power was provided by the Argonne Leadership Computing Facility (ALCF) and the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. CNM, ALCF and NERSC are all DOE Office of Science User Facilities.

The original discovery occurred when Erdemir and Eryilmaz decided to see what would happen when a small steel ring was coated with a catalytically active nanocoating – tiny molecules of metals that promote chemical reactions to break down other materials – then subjected to high pressure and heat using a base oil without the complex additives of modern lubricants. When they looked at the ring after the endurance test, they didn’t see the expected rust and surface damage, but an intact ring with an odd blackish deposit on the contact area.

“This test creates extreme contact pressure and temperatures, which are supposed to cause the ring to wear and eventually seize,” said Eryilmaz. “But this ring didn’t significantly wear and this blackish deposit was visible. We said, ‘This material is strange. Maybe this is what is causing this unusual effect.'”

Looking at the deposit using high-powered optical and laser Raman microscopes, the experimentalists realized the deposit was a tribofilm of diamond-like carbon, similar to several other DLCs developed at Argonne in the past. But it worked even better. Tests revealed the DLC tribofilm reduced friction by 25 to 40 percent and that wear was reduced to unmeasurable values.

Further experiments, led by postdoctoral researcher Giovanni Ramirez, revealed that multiple types of catalytic coatings can yield DLC tribofilms. The experiments showed the coatings interact with the oil molecules to create the DLC film, which adheres to the metal surfaces. When the tribofilm is worn away, the catalyst in the coating is re-exposed to the oil, causing the catalysis to restart and develop new layers of tribofilm. The process is self-regulating, keeping the film at consistent thickness. The scientists realized the film was developing spontaneously between the sliding surfaces and was replenishing itself, but they needed to understand why and how.

To provide the theoretical understanding of what the tribology team was seeing in its experiments, they turned to Sankaranarayanan and Narayanan, who used the immense computing power of ALCF’s 10-petaflop supercomputer, Mira. They ran large-scale simulations to understand what was happening at the atomic level, and determined that the catalyst metals in the nanocomposite coatings were stripping hydrogen atoms from the hydrocarbon chains of the lubricating oil, then breaking the chains down into smaller segments. The smaller chains joined together under pressure to create the highly durable DLC tribofilm.

“This is an example of catalysis under extreme conditions created by friction. It is opening up a new field where you are merging catalysis and tribology, which has never been done before,” said Sankaranarayanan. “This new field of tribocatalysis has the potential to change the way we look at lubrication.”

The theorists explored the origins of the catalytic activity to understand how catalysis operates under the extreme heat and pressure in an engine. By gaining this understanding, they were able to predict which catalysts would work, and which would create the most advantageous tribofilms.

“Interestingly, we found several metals or composites that we didn’t think would be catalytically active, but under these circumstances, they performed quite well,” said Narayanan. “This opens up new pathways for scientists to use extreme conditions to enhance catalytic activity.”

The implications of the new tribofilm for efficiency and reliability of engines are huge. Manufacturers already use many different types of coatings — some developed at Argonne — for metal parts in engines and other applications. The problem is those coatings are expensive and difficult to apply, and once they are in use, they only last until the coating wears through. The new catalyst allows the tribofilm to be continually renewed during operation.

Additionally, because the tribofilm develops in the presence of base oil, it could allow manufacturers to reduce, or possibly eliminate, some of the modern anti-friction and anti-wear additives in oil. These additives can decrease the efficiency of vehicle catalytic converters and can be harmful to the environment because of their heavy metal content.

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

Carbon-based tribofilms from lubricating oils by Ali Erdemir, Giovanni Ramirez, Osman L. Eryilmaz, Badri Narayanan, Yifeng Liao, Ganesh Kamath, & Subramanian K. R. S. Sankaranarayanan. Nature 536, 67–71 (04 August 2016) doi:10.1038/nature18948 Published online 03 August 2016

This paper is behind a paywall.

Generating clean fuel with individual gold atoms

A July 22, 2016 news item on Nanowerk highlights an international collaboration focused on producing clean fuel,

A combined experimental and theoretical study comprising researchers from the Chemistry Department and LCN [London Centre for Nanotechnology], along with groups in Argentina, China, Spain and Germany, has shed new light on the behaviour of individual gold atoms supported on defective thin cerium dioxide films – an important system for catalysis and the generation of clean hydrogen for fuel.

A July ??, 2016 LCN press release, which originated the news item, expands on the theme of catalysts, the research into individual gold atoms, and how all this could result in clean fuel,

Catalysis plays a vital role in our world; an estimated 80% of all chemical and materials are made via processes which involve catalysts, which are commonly a mixture of metals and oxides. The standard motif for these heterogeneous catalysts (where the catalysts are solid and the reactants are in the gas phase) is of a high surface area oxide support that is decorated with metal nanoparticles a few nanometres in diameter. Cerium dioxide (ceria, CeO2) is a widely used support material for many important industrial processes; metal nanoparticles supported on ceria have displayed high activities for applications including car catalytic converters, alcohol synthesis, and for hydrogen production. There are two key attributes of ceria which make it an excellent active support material: its oxygen storage and release ability, and its ability to stabilise small metal particles under reaction conditions. A recent system that has been the focus of much interest has been that of gold nanoparticles and single atoms with ceria, which has demonstrated high activity towards the water-gas-shift reaction, (CO + H2O —> CO2 + H2) a key stage in the generation of clean hydrogen for use in fuel cells.

The nature of the active sites of these catalysts and the role that defects play are still relatively poorly understood; in order to study them in a systematic fashion, the researchers prepared model systems which can be characterised on the atomic scale with a scanning tunnelling microscope.

Figure: STM images of CeO2-x(111) ultrathin films before and after the deposition of Au single atoms at 300 K. The bright lattice is from the oxygen atoms at the surface – vacancies appear as dark spots

These model systems comprised well-ordered, epitaxial ceria films less than 2 nm thick, prepared on a metal single crystal, upon which single atoms and small clusters of gold were evaporated onto under ultra-high-vacuum (essential to prevent contamination of the surfaces). Oxygen vacancy defects – missing oxygen atoms in the top layer of the ceria – are relatively common at the surface and appear as dark spots in the STM images. By mapping the surface before and after the deposition of gold, it is possible to analyse the binding of the metal atoms, in particular there does not appear to be any preference for binding in the vacancy sites at 300 K.

Publishing their results in Physical Review Letters, the researchers combined these experimental results with theoretical studies of the binding energies and diffusion rates across the surface. They showed that kinetic effects governed the behaviour of the gold atoms, prohibiting the expected occupation of the thermodynamically more stable oxygen vacancy sites. They also identified electron transfer between the gold atoms and the ceria, leading to a better understanding of the diffusion phenomena that occur at this scale, and demonstrated that the effect of individual surface defects may be more minor than is normally imagined.

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

Diffusion Barriers Block Defect Occupation on Reduced CeO2(111) by P.G. Lustemberg, Y. Pan, B.-J. Shaw, D. Grinter, Chi Pang, G. Thornton, Rubén Pérez, M. V. Ganduglia-Pirovano, and N. Nilius. Phys. Rev. Lett. Vol. 116, Iss. 23 — 10 June 2016 2016DOI:http://dx.doi.org/10.1103/PhysRevLett.116.236101 Published 9 June 2016

This paper is behind a paywall.

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.

Training your bacterium to perform photosynthesis

A Jan. 4, 2016 news item on Nanotechnology Now announces a rather distinctive approach to artificial photosynthesis,

Trainers of dogs, horses, and other animal performers take note: a bacterium named Moorella thermoacetica has been induced to perform only a single trick, but it’s a doozy. Berkeley Lab researchers are using M. thermoacetica to perform photosynthesis – despite being non-photosynthetic – and also to synthesize semiconductor nanoparticles in a hybrid artificial photosynthesis system for converting sunlight into valuable chemical products.

“We’ve demonstrated the first self-photosensitization of a non-photosynthetic bacterium, M. thermoacetica, with cadmium sulfide nanoparticles to produce acetic acid from carbon dioxide at efficiencies and yield that are comparable to or may even exceed the capabilities of natural photosynthesis,” says Peidong Yang, a chemist with Berkeley Lab’s Materials Sciences Division, who led this work.

“The bacteria/inorganic-semiconductor hybrid artificial photosynthesis system we’ve created is self-replicating through the bio-precipitation of cadmium sulfide nanoparticles, which serve as the light harvester to sustain cellular metabolism,” Yang says. “Demonstrating this cyborgian ability to self-augment the functionality of biological systems through inorganic chemistry opens up the integration of biotic and abiotic components for the next generation of advanced solar-to-chemical conversion technologies.”

A Jan. 1, 2016 Berkeley Lab news release, which originated the news item, provides a little more detail,

Photosynthesis is the process by which nature harvests sunlight and uses the solar energy to synthesize carbohydrates from carbon dioxide and water. Artificial versions of photosynthesis are being explored for the clean, green and sustainable production of chemical products now made from petroleum, primarily fuels and plastics. Yang and his research group have been at the forefront of developing artificial photosynthetic technologies that can realize the full potential of solar-to-chemical synthesis.

“In our latest study, we combined the highly efficient light harvesting of an inorganic semiconductor with the high specificity, low cost, and self-replication and self-repair of a biocatalyst,” Yang says. “By inducing the self-photosensitization of M. thermoacetica with cadmium sulfide nanoparticles, we enabled the photosynthesis of acetic acid from carbon dioxide over several days of light-dark cycles at relatively high quantum yields, demonstrating a self-replicating route toward solar-to-chemical carbon dioxide reduction.”

Cadmium sulfide is a well-studied semiconductor with a band structure and that is well-suited for photosynthesis. As both an “electrograph” (meaning it can undergo direct electron transfers from an electrode), and an “acetogen” (meaning it can direct nearly 90-percent of its photosynthetic products towards acetic acid), M. thermoacetica serves as the ideal model organism for demonstrating the capabilities of this hybrid artificial photosynthesis system.

“Our hybrid system combines the best of both worlds: the light-harvesting capabilities of semiconductors with the catalytic power of biology,” Yang says. “In this study, we’ve demonstrated not only that biomaterials can be of sufficient quality to carry out useful photochemistry, but that in some ways they may be even more advantageous in biological applications.”

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

Self-photosensitization of nonphotosynthetic bacteria for solar-to-chemical production by Kelsey K. Sakimoto, Andrew Barnabas Wong, Peidong Yang. Science 1 January 2016: Vol. 351 no. 6268 pp. 74-77 DOI: 10.1126/science.aad3317

This paper is behind a paywall.

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.

An enzyme’s atoms are in a subtle dance that can affect protein function

This research comes from Québec’s Institut national de la recherche scientifique (INRS) according to a Dec. 10, 2015 news item on ScienceDaily,

Infinitesimal fluctuations occurring on the milli- and even nano-second time scales within the three-dimensional structure of enzymes may be one of the keys to explaining protein function. Professor Nicolas Doucet’s team at INRS has demonstrated that even when certain amino acids are far from the active site of an enzyme, a change in their flexibility and atomic fluctuations can significantly impact enzyme activity. This phenomenon, which has been underestimated up to now, could explain certain protein engineering failures and help improve the way synthetic functional enzymes are designed.

A Dec. 10, 2015 INRS news release on EurekAlert, which originated the news item, provides an explanation of an enzyme’s functions and what the researchers found out,

Enzymes are nanomachines that are exceptionally efficient at catalyzing a chemical reaction. They play a role in all cellular mechanisms. Like all proteins, they are made up of amino acid chains that are folded and assembled in a very precise 3D structure. Some enzymes, like ribonuclease A, are so efficient that they catalyze the transformation of chemical molecules thousands of times per second.

In this study, Donald Gagné, a researcher in Professor Doucet’s lab holding a PhD in biology from INRS, analyzed the impact of removing a methyl group located near a loop distant from the reaction site of ribonuclease A–a very slight change that presumably would have no effect. The mutation does not perturb the 3D structure of the enzyme. However, it did result in a four-fold reduction in the affinity of ribonuclease A for nucleotides (molecules to which it must bind to carry out its function). How is this possible?

Using crystallography techniques and nuclear magnetic resonance to examine the enzyme at atomic resolution, Donald Gagné compared normal ribonuclease A with the mutated enzyme. He observed that when ribonuclease A is modified, the nucleotides do not position themselves correctly and have a harder time binding to the active site. It appears that this repositioning is due to an increase in enzyme fluctuations caused by the elimination of this distant methyl group, which we can picture as creating vibrations that spread through the enzyme structure all the way to the site of catalysis.

This demonstration of the importance of enzyme dynamics could change our understanding of protein and enzyme mechanisms. While it remains a challenge to measure fluctuations at this atomic scale, researchers have studied the three-dimensional structure of proteins to understand how they function. Despite the staggering complexity of this phenomenon, we now know that proteins are increasingly regulated by the subtle dance of their atoms.

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

Perturbation of the Conformational Dynamics of an Active-Site Loop Alters Enzyme Activity by Donald Gagné, Rachel L. French, Chitra Narayanan, Miljan Simonović, Pratul K. Agarwal, Nicolas Doucet. Structure Volume 23, Issue 12, p2256–2266, 1 December 2015 DOI: http://dx.doi.org/10.1016/j.str.2015.10.011

This paper is behind a paywall.