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Blinded by Light, Copper Resists Rust

Wednesday, May 22, 2013

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Intense light can cancel out rust-forming properties on copper, yielding an environmentally friendly way to create propylene oxide, the basis for many coatings, engineers from the University of Michigan have discovered.

Using white light five times the sun's strength, copper nanoparticles can act as a catalyst by resisting oxidation, allowing oxygen molecules to bind with propylene molecules to form propylene oxide.

"We report a new physical phenomenon that has potentially significant practical implications," Suljo Linic, an associate professor of chemical engineering who led the study, said in a news release from the university.

University of Michigan
Photos: Joseph Xu, Michigan Engineering Communications & Marketing

A light five times as intense as the sun can keep copper from rusting, potentially providing a cheap and environmentally friendly way to make propylene oxide.

Propylene oxide is a precursor for paint, insulating foams, plastics and many other household products. The United States produces over 2.4 million metric tons of propylene oxide each year, making it a $4.9 billion market, according to the university.

However, the process used to make about half of the propylene oxide in the U.S. also generates about twice as much salt.

With a new kind of reactor that can illuminate the catalyst, this new method of making propylene oxide could be a cheap and environmentally friendly solution for the industry, the scientists say.

Seeking the 'Holy Grail'

The search for the "holy grail" of catalysis—one that can form propylene oxide in a direct reaction and avoid waste—has shied away from metallic copper because it usually binds to oxygen and forms copper oxide, which has poor catalytic properties.

As copper oxide, the substance will break propylene down into carbon dioxide or attach oxygen to only one atom. But in its metallic state, copper prefers to bind oxygen with two of the propylene's carbon atoms, resulting in propylene oxide.

When carefully structured, light can be used to reverse copper oxidation, the researchers found. To put it to the test, the team made copper nanoparticles about 40 nanometers across, put the nanoparticles on tiny particles of clear silica, then floated propylene and oxygen gas over copper/silica dust.

When left in the dark, the copper oxidized and only 20 percent of the gas converted to propylene oxide. But when the team used the intense white light, the copper stayed in its metallic state and turned 50 percent of the gas into propylene oxide.

Scratching a Unique Structure Surface

"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 the first author on the paper.

propylene oxide

The test reactor holds the catalyst and exposes it to oxygen and propylene gases. When the reactor is closed, a light shines down from the top, which allows the copper to keep oxygen off its surface. The copper instead binds the propylene and oxygen.

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

Although the surface of the copper was already oxidized, the metallic copper underneath concentrated the light, freeing the electrons from the copper atoms. The electrons then broke the bonds between the copper and oxygen.

"We are just scratching the surface," Linic said. "I can envision many proceses 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."

"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.

Publication and Funding

The study, "Tuning Selectivity in Propylene Epoxidation by Plasmon Mediated Photo-Switching of Cu Oxidation State," was published in the March 29 issue of Science.

The paper was authored by Andiappan, Linic, and Jianwen Zhang, a former chemical engineering graduate student.

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 looking for commercialization partners.

   

Tagged categories: Carbon dioxide; Copper; Polypropylene; Research; Rust

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