Redox Properties of Cu2O(100) and (111) Surfaces

Wang, Chunlei; Tissot, Heloise; Escudero, Carlos; Pérez-Dieste, Virginia; Stacchiola, Dario; Weissenrieder, Jonas

doi:10.1021/acs.jpcc.8b08494

Title: Redox Properties of Cu₂O(100) and (111) Surfaces

Journal Article · Mon Nov 19 00:00:00 EST 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b08494· OSTI ID:1492774

Wang, Chunlei ^[1]; Tissot, Heloise ^[1];

^[2]; Pérez-Dieste, Virginia ^[2];

^[3];

^[1]

KTH Royal Inst. of Technology, Stockholm (Sweden)
Alba Synchrotron Light Source, Barcelona (Spain)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Intense research efforts are directed towards Cu and Cu₂O based catalysts as they are viewed as potential replacements for noble metal catalysts. However, applications are complicated by deactivation, e.g. through complete oxidation to CuO. Despite the importance of the redox processes for Cu₂O catalysts a molecular level understanding of the deactivation process is still lacking. Therefore we study the initial stages of oxidization of well-defined Cu₂O bulk single crystals of (100) and (111) termination by means of synchrotron radiation X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM). Exposure of the (100) surface to 1 mbar O₂ at 25 °C result in formation of a 1.0 monolayers (ML) CuO surface oxide. The surface is also covered by 0.7 ML OH groups from unavoidable trace moisture in reaction gas. In contrast, neither hydroxylation nor oxidation was observed on the (111) surface under similar exposure conditions. On (111) the formation of CuO did only commence after annealing to ~400 °C in 1 mbar O₂, highlighting the different character of the two surfaces. Annealing of the (100) surface, under ultrahigh vacuum conditions, to temperatures up to ~225 °C resulted in removal of the OH groups (0.46 ML decrease) at a rate similar to a detected increase in CuO coverage (0.45 ML increase), suggesting the reaction path 2OH_adsorbed + Cu₂O_solid → H₂O_gas + 2CuO_solid. STM was used to correlate the observed changes in surface chemistry with surface morphology, confirming the surface hydroxylation and CuO formation. The STM analysis showed dramatic changes in surface morphology demonstrating a high mobility of the active species under reaction conditions.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1492774

Report Number(s):: BNL-210924-2019-JAAM

Journal Information:: Journal of Physical Chemistry. C, Vol. 122, Issue 50; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 23 works

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