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Scientists Use Peroxide to Peer into Metal Oxide Reactions

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Researchers at Binghamton University led research partnering with the Center for Functional Nanomaterials (CFN)—a U.S. Department of Energy (DOE) Office of Science User Facility at Brookhaven National Laboratory—to get a better look at how peroxides on the surface of copper oxide promote the oxidation of hydrogen but inhibit the oxidation of carbon monoxide, allowing them to steer oxidation reactions. They were able to observe these quick changes with two complimentary spectroscopy methods that have not been used in this way. The results of this work have been published in the journal Proceedings of the National Academy of Sciences (PNAS).

“Copper is one of the most studied and relevant surfaces, both in catalysis and in corrosion science,” explained Anibal Boscoboinik, materials scientist at CFN. “So many mechanical parts that are used in industry are made of copper, so trying to understand this element of the corrosion processes is very important.”

“I’ve always liked looking at copper systems,” said Ashley Head also a materials scientist at CFN. “They have such interesting properties and reactions, some of which are really striking.”

Gaining a better understanding of oxide catalysts gives researchers more control of the chemical reactions they produce, including solutions for clean energy. Copper, for example, can catalytically form and convert methanol into valuable fuels, so being able to control the amount of oxygen and number of electrons on copper is a key step to efficient chemical reactions.
Peroxides are chemical compounds that contain two oxygen atoms linked by shared electrons. The bond in peroxides is fairly weak, allowing other chemicals to alter its structure, which makes them very reactive. In this experiment, scientists were able to alter the redox steps of catalytic oxidation reactions on an oxidized copper surface (CuO) by identifying the makeup of peroxide species formed with different gases: ­O2 (oxygen), H2 (hydrogen), and CO (carbon monoxide).

Redox is a combination of reduction and oxidation. In this process, the oxidizing agent gains an electron and the reducing agent loses an electron. When comparing these different peroxide species and how these steps played out, researchers found that a surface layer of peroxide significantly enhanced CuO reducibility in favor of H2 oxidation. They also found that, on the other hand, it acted as an inhibitor to suppress CuO reduction against CO (carbon monoxide) oxidation. They found that this opposite effect of the peroxide on the two oxidation reactions stems from the modification of the surface sites where the reaction takes place.