Tuning the surface reactivity of oxides by peroxide species

Zhu, Yaguang; Wang, Jianyu; Patel, Shyam Bharatkumar; Li, Chaoran; Head, Ashley R.; Boscoboinik, Jorge Anibal; Zhou, Guangwen

doi:10.1073/pnas.2215189120

Title: Tuning the surface reactivity of oxides by peroxide species

Journal Article · Tue Mar 21 00:00:00 EDT 2023 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2215189120· OSTI ID:1962691

Zhu, Yaguang ^[1]; Wang, Jianyu ^[1];

^[1]; Li, Chaoran ^[1]; Head, Ashley R. ^[2];

^[2];

^[1]

Department of Mechanical Engineering &, Materials Science and Engineering Program, State University of New York, Binghamton, NY 13902
Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY 11973

The Mars–van Krevelen mechanism is the foundation for oxide-catalyzed oxidation reactions and relies on spatiotemporally separated redox steps. In this work, we demonstrate the tunability of this separation with peroxide species formed by excessively adsorbed oxygen, thereby modifying the catalytic activity and selectivity of the oxide. Using CuO as an example, we show that a surface layer of peroxide species acts as a promotor to significantly enhance CuO reducibility in favor of H₂ oxidation but conversely as an inhibitor to suppress CuO reduction against CO oxidation. Together with atomistic modeling, we identify that this opposite effect of the peroxide on the two oxidation reactions stems from its modification on coordinately unsaturated sites of the oxide surface. By differentiating the chemical functionality between lattice oxygen and peroxide, these results are closely relevant to a wide range of catalytic oxidation reactions using excessively adsorbed oxygen to activate lattice oxygen and tune the activity and selectivity of redox sites.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Binghamton Univ., NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0001135; SC0012704

OSTI ID:: 1962691

Alternate ID(s):: OSTI ID: 1987696; OSTI ID: 1991229

Report Number(s):: BNL-224556-2023-JAAM; e2215189120

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 120 Journal Issue: 13; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
metal oxide
peroxide
infrared reflection absorption spectroscopy (IRRAS)
ambient-pressure X-ray photoelectron spectroscopy (APXPS)
reducibility
surface reactivity
36 MATERIALS SCIENCE

Title: Tuning the surface reactivity of oxides by peroxide species

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