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Chemical engineering graduate student Marimuthu Andiappan presents the copper catalyst in a vial. The nanoparticles are embedded in silica, resulting in a whitish dust.Wouldn't it be convenient if you could reverse the rusting of your car by shining a bright light on it? It turns out that this concept works for undoing oxidation on copper nanoparticles, and it could lead to an environmentally friendly production process for an important industrial chemical, University of Michigan engineers have discovered.

"We report a new physical phenomenon that has potentially significant practical implications," said Suljo Linic, an associate professor of chemical engineering, who led the study, which is published in the March 29 issue of Science.

Copper's newfound ability to shake off oxygen attached to its surface could allow it to act as a catalyst for a long-sought reaction, causing oxygen molecules to bind with propylene molecules in the way that forms propylene oxide. Propylene oxide is a precursor for making many plastics, toiletries and other household products such as antifreeze, paints and insulating foams. To meet demand for these products, the U.S. produces more than 2.4 million metric tons of propylene oxide per year, worth about $4.9 billion.

Unfortunately, producing propylene oxide involves a complex chain of reactions that generate unwanted chemicals. The process that provides about half of the propylene oxide in the U.S. also produces about twice as many tons of salt.

A catalyst that can coax propylene and oxygen to form propylene oxide in a direct reaction, avoiding the waste, has been called a "holy grail" of catalysis. Metallic copper showed promise, but it had—until now—been written off because it tends to bind itself to oxygen, forming copper oxide, which has poor catalytic properties.

"Copper in metallic form has this unique electronic structure that activates the reaction pathway for propylene oxide more than the undesired pathways," said Marimuthu Andiappan, a graduate student in chemical engineering and first author on the paper.

Metallic copper prefers to bind oxygen with two of the propylene's carbon atoms, forming propylene oxide. Copper oxide, on the other hand, tends to break the propylene down into carbon dioxide or attach the oxygen to only one carbon atom, resulting in the herbicide acrolein.

However, Andiappan, Linic, and former chemical engineering graduate student Jianwen Zhang found that if copper is cleverly structured, light can reverse its oxidation. The team made copper nanoparticles about 40 nanometers across, or roughly one-hundredth of the thickness of a strand of spider silk. They peppered tiny particles of clear silica with the nanoparticles and then floated a gas of propylene and oxygen over the resulting dust.

Metal catalyst in open reactor

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A metal nanoparticle catalyst sits in the open reactor with two gas lines connected. Photo: Joseph Xu, Communications & Marketing. All rights reserved.

Gas pumps and tanks

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The three pumps connect to the three gas tanks in the background. Only two pumps, one moving oxygen and the other moving propylene gas, operated during the experiment. With the help of the copper catalyst, the gasses combine into the industrially important chemical propylene oxide. Photo: Joseph Xu, Communications & Marketing. All rights reserved.

Adjusting the light

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Marimuthu Andiappan, a chemical engineering graduate student, adjusts the light over the reactor. The light shines with 5 times the sun's intensity and helps the copper nanoparticles get rid of oxygen atoms that bind to them. Photo: Joseph Xu, Communications & Marketing. All rights reserved.

Adjusting the temperature

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Andiappan adjusts the temperature of the reactor (by degrees Celsius). Photo: Joseph Xu, Communications & Marketing. All rights reserved.

Quick measurements

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For quick measurements of the reaction products, Andiappan uses spectrometers. These devices identify molecules by their masses or by the patterns of light they absorb and emit. Photo: Joseph Xu, Communications & Marketing. All rights reserved.

Reaction results

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Andiappan studies the results from a gas chromatograph. The device gives very accurate measurements of the reaction products, but it is very slow - the gas is sorted into clouds of its constituent molecules as it flows through a long tube. Suljo Linic, an associate professor of chemical engineering, supervises. Photo: Joseph Xu, Communications & Marketing. All rights reserved.

In the dark, the copper oxidized, and only 20 percent of the gas converted to propylene oxide. But under white light, five times the sun's intensity, the copper stayed in the metallic state and turned 50 percent of the propylene into propylene oxide.

"To our knowledge, this is the first time anyone has shown that light can be used to switch the oxidation state from an oxide to a metallic state," Andiappan said.

The metallic copper under the oxidized surface concentrated the light, freeing electrons from copper atoms. Those electrons then broke the bonds between the copper and oxygen.

A new kind of reactor that can illuminate the catalyst will be needed to bring this potentially cheap and environmentally friendly way of making propylene oxide to industry.

"Theoretically, it is possible to use mirrors to focus sunlight and get this much intensity," Andiappan said.

"We are just scratching the surface," Linic said. "I can envision many processes that wouldn't be possible with conventional strategies, where changing the oxidation state during the reaction or driving reactions with light could affect the outcome dramatically."

The paper describing this work is titled "Tuning selectivity in propylene epoxidation by plasmon mediated photo-switching of Cu oxidation state." Read the abstract.

The study was funded by the Department of Energy and the National Science Foundation. The university is pursuing patent protection for the intellectual property, and is seeking commercialization partners to help bring the technology to market.

Article topics: Nano-Catalysts


About Michigan Engineering: The University of Michigan College of Engineering is one of the top engineering schools in the country. Eight academic departments are ranked in the nation's top 10 -- some twice for different programs. Its research budget is one of the largest of any public university. Its faculty and students are making a difference at the frontiers of fields as diverse as nanotechnology, sustainability, healthcare, national security and robotics. They are involved in spacecraft missions across the solar system, and have developed partnerships with automotive industry leaders to transform transportation. Its entrepreneurial culture encourages faculty and students alike to move their innovations beyond the laboratory and into the real world to benefit society. Its alumni base of nearly 70,000 spans the globe.

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