Understanding how defects and dopant atoms in copper surface oxides affect reactivity

Lal, Vinita; Dannar, Audrey; Sykes, E. Charles H.

doi:10.1016/j.apsusc.2025.165520

Understanding how defects and dopant atoms in copper surface oxides affect reactivity

Journal Article · Sun Dec 07 00:00:00 EST 2025 · Applied Surface Science

DOI:https://doi.org/10.1016/j.apsusc.2025.165520· OSTI ID:3009064

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Tufts Univ., Medford, MA (United States)

Copper and its oxides are key catalytic materials, on which reactions often occur at the metal/oxide interface. Here, in this work, we directly connect the induction period observed during methanol-driven reduction of thin-film copper oxides to their atomic-scale structural order. Using temperature-programmed desorption (TPD) methanol titrations combined with scanning tunneling microscopy, we show that highly ordered oxide phases – particularly the “29” structure with its low defect density – exhibit long induction periods and initially low reactivity. The induction period, defined as the number of methanol TPD cycles required to reach half of the maximum formaldehyde yield, scales with oxide order and oxygen coverage. Enhanced reactivity of well-ordered oxides emerges only after repeated methanol adsorption/desorption cycles generate oxygen vacancies and new Cu(111)/Cu_xO interfacial sites. In contrast, disordered or sub-stoichiometric oxides, which contain more intrinsic defects and interfaces, are active from the first TPD cycle. We further examine how dilute Pt and Rh dopants influence oxide order and reactivity: 1% Pt increases defect density and catalytic activity, while 1% Rh promotes oxide ordering and longer induction periods. These findings demonstrate that dilute alloying provides a potential method for tuning the structure and reactivity of Cu(111)/Cu_xO interfaces.

View Accepted Manuscript (DOE)

Research Organization:: Tufts Univ., Medford, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021196

OSTI ID:: 3009064

Journal Information:: Applied Surface Science, Journal Name: Applied Surface Science Vol. 722; ISSN 0169-4332

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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