Redox Properties of Cu2O(100) and (111) Surfaces
Abstract
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 tomore »
- Authors:
-
[2];
[3];
[1]
- KTH Royal Inst. of Technology, Stockholm (Sweden)
- Alba Synchrotron Light Source, Barcelona (Spain)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1492774
- Report Number(s):
- BNL-210924-2019-JAAM
Journal ID: ISSN 1932-7447
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 50; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wang, Chunlei, Tissot, Heloise, Escudero, Carlos, Pérez-Dieste, Virginia, Stacchiola, Dario, and Weissenrieder, Jonas. Redox Properties of Cu2O(100) and (111) Surfaces. United States: N. p., 2018.
Web. doi:10.1021/acs.jpcc.8b08494.
Wang, Chunlei, Tissot, Heloise, Escudero, Carlos, Pérez-Dieste, Virginia, Stacchiola, Dario, & Weissenrieder, Jonas. Redox Properties of Cu2O(100) and (111) Surfaces. United States. https://doi.org/10.1021/acs.jpcc.8b08494
Wang, Chunlei, Tissot, Heloise, Escudero, Carlos, Pérez-Dieste, Virginia, Stacchiola, Dario, and Weissenrieder, Jonas. Mon .
"Redox Properties of Cu2O(100) and (111) Surfaces". United States. https://doi.org/10.1021/acs.jpcc.8b08494. https://www.osti.gov/servlets/purl/1492774.
@article{osti_1492774,
title = {Redox Properties of Cu2O(100) and (111) Surfaces},
author = {Wang, Chunlei and Tissot, Heloise and Escudero, Carlos and Pérez-Dieste, Virginia and Stacchiola, Dario and Weissenrieder, Jonas},
abstractNote = {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 2OHadsorbed + Cu2Osolid → H2Ogas + 2CuOsolid. 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.},
doi = {10.1021/acs.jpcc.8b08494},
journal = {Journal of Physical Chemistry. C},
number = 50,
volume = 122,
place = {United States},
year = {Mon Nov 19 00:00:00 EST 2018},
month = {Mon Nov 19 00:00:00 EST 2018}
}
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