Carbon monoxide is a colorless, odorless and dangerous gas produced by cars, trucks and other vehicles that burn fossil fuels. Exhaust systems use a catalytic converter to change that carbon monoxide into nontoxic carbon dioxide, but according to the U.S. Environmental Protection Agency, fuel-burning vehicles are the greatest source of carbon monoxide emissions in the atmosphere, adding to the abundance of greenhouse gases in the air.
Scientists around the world are working to reduce those emissions, and one way of doing so is to learn more about the chemical reactions that occur inside the exhaust system. Those reactions often use gold as a catalyst. While large amounts of gold are inert, tiny particles of it are an active catalyst in the oxidization of carbon monoxide, a reaction that changes it into carbon dioxide.
“If we can better understand how this catalysis works, we can optimize and improve it. If we can better engineer the catalysts, we can control or limit the carbon monoxide.” — Florian Meneau, physicist, Brazilian Synchrotron Light Source.
Aline Passos and Florian Meneau have been studying that reaction for years. Both work at the Brazilian Synchrotron Light Laboratory (LNLS), Passos as a chemist and Meneau as a physicist. Together they lead a research team that recently used the ultrabright X-rays of the Advanced Photon Source (APS), a U.S. Department of Energy (DOE) Office of Science User Facility at the DOE’s Argonne National Laboratory, to illuminate tiny particles of gold as they catalyzed a similar reaction to the one that happens inside a car’s exhaust. The results of this research were published in Nature Communications.
“If we can better understand how this catalysis works, we can optimize and improve it,” Passos said. “If we can better engineer the catalysts, we can control or limit the carbon monoxide.”
The properties of this reaction are well known, Passos and Meneau said, but studying the reaction of a single small gold particle as it undergoes this reaction is new scientific territory, and only possible because of the technology available at the APS.
To conduct this experiment, Passos synthesized gold nanoparticles, about 60 nanometers in diameter. (For scale, a sheet of paper is about 100,000 nanometers thick.) She constructed them in two shapes, spheres and cubes, and introduced some chemical defects to some of the particles, changing the atomic structure slightly to see if that affected the way they catalyzed the reaction.
”The atoms in different positions change, and they change the electronic and chemical properties,” Meneau said. “It’s well known how to do this. But we had only been able to examine the catalysis stage before. We have not been able to observe what changes inside a single particle during the reaction.”
To accomplish this, the Brazilian team then brought these particles to beamline 34-ID-C at the APS, which specializes in what is called “in situ” imaging experiments. This means the APS X-ray beams can be used to take pictures of samples while they are undergoing reactions — changes in temperature, for instance, or increased pressure — in real time. In this case, scientists used the gold nanoparticles to oxidize carbon monoxide and captured the changes in the crystalline framework of the particles as the reaction was happening.
Wonsuk Cha, an assistant physicist with Argonne’s X-ray Science Division (XSD) and a co-author on the paper, has been working for years on in situ experiments at this beamline. The challenge, he says, has been developing chambers for the experiments that are compatible with the imaging technique.
“One of the challenges is the small size of the samples we work with,” he said. “The beam size is typically 500 nanometers wide, and we have perfected techniques for monitoring the sample’s position within the beam, which enables the experiment to keep going.”
The technique used in this experiment is called coherent X-ray diffraction imaging (CDI), and Ross Harder, a physicist with XSD, has been the lead developer of instrumentation for that technique at Argonne since 2008. For CDI experiments, the X-ray beam diffracts off of the sample and projects a pattern of information on a detector, and computer algorithms are then used to interpret that information and construct an image from it.
“We can see nanoscale images that we can’t see with a regular light,” Harder said. “There are only a handful of light sources in the world capable of doing this experiment.”
The result, Meneau said, is a new picture of the way these nanoparticles experience catalytic reactions. The image that emerged is a map of the strain in the particle — a measure of the change of shape when the sample undergoes stress — to the corners and edges, showing that these parts of the nanoparticles are most involved in the catalysis.
The data also show that the strain can be affected by induced chemical changes, and that identically shaped and sized nanoparticles do not experience this reaction the same way. This means that the reaction itself can potentially be changed on a chemical level by altering the catalyst.
While samples of the size used in this experiment might seem small, the typical size for a gold catalyst in industrial applications is five nanometers thick, about the width of two strands of human DNA. Passos and Meneau said that the next step for their research is to scale it down, with the goal of capturing the catalytic reaction in smaller and smaller samples.
A massive upgrade project underway at the APS will allow for this scaling down, they said, as will the new light source at LNLS, Sirius, which is scheduled to go online in 2021. The APS Upgrade will increase the brightness and coherent flux by 100 to 1,000 times compared to the current APS, which will improve the quality of diffraction images.
“Sixty nanometers is way too large for industry,” Meneau said, “but the APS Upgrade will let us investigate smaller samples. The new machines can do this.”
About the Advanced Photon Source
The U. S. Department of Energy Office of Science’s Advanced Photon Source (APS) at Argonne National Laboratory is one of the world’s most productive X-ray light source facilities. The APS provides high-brightness X-ray beams to a diverse community of researchers in materials science, chemistry, condensed matter physics, the life and environmental sciences, and applied research. These X-rays are ideally suited for explorations of materials and biological structures; elemental distribution; chemical, magnetic, electronic states; and a wide range of technologically important engineering systems from batteries to fuel injector sprays, all of which are the foundations of our nation’s economic, technological, and physical well-being. Each year, more than 5,000 researchers use the APS to produce over 2,000 publications detailing impactful discoveries, and solve more vital biological protein structures than users of any other X-ray light source research facility. APS scientists and engineers innovate technology that is at the heart of advancing accelerator and light-source operations. This includes the insertion devices that produce extreme-brightness X-rays prized by researchers, lenses that focus the X-rays down to a few nanometers, instrumentation that maximizes the way the X-rays interact with samples being studied, and software that gathers and manages the massive quantity of data resulting from discovery research at the APS.
This research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.
Argonne National Laboratory seeks solutions to pressing national problems in science and technology. The nation’s first national laboratory, Argonne conducts leading-edge basic and applied scientific research in virtually every scientific discipline. Argonne researchers work closely with researchers from hundreds of companies, universities, and federal, state and municipal agencies to help them solve their specific problems, advance America’s scientific leadership and prepare the nation for a better future. With employees from more than 60 nations, Argonne is managed by UChicago Argonne, LLC for the U.S. Department of Energy’s Office of Science.
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