Potassium-induced effect on structure and chemical activity of CuxO/Cu(111) (x≤2) surface: A combined scanning tunneling microscopy and density functional theory study
Abstract
Potassium (K) plays an essential role to promote catalytic reactions in many established industrial catalytic processes. Here in this paper, we report a combined study using STM and DFT to understand the effect of the deposition of K on the atomic and electronic structures as well as chemical activities of CuxO/Cu(111) (x≤2). The DFT calculations show a pseudomorphic growth of K on CuxO/Cu(111) up to 0.19 monolayer (ML) of coverage, in which K binds the surface by a strong ionic interaction with chemisorbed oxygen and relatively weak electrostatic interactions with Cu ions, the lower and upper oxygen atoms on the CuxO rings. The simulated STM pattern based on the DFT results agrees well with the experimental observations. The deposited K has a great impact on the surface electronic structure of CuxO/Cu(111), which induces a significant reduction in the work function and leads to a strong electron polarization on the surface. The promotion of K on the surface binding properties is selective and varies depending on the nature of the adsorbates. According to our results, K has little effect on surface acidity but it enhances the surface basicity significantly. Consequently, the presence of K does not help CO adsorption on CuxO/Cu(111)more »
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States); Shanghai Univ. of Engineering Science, Shanghai (China)
- Stony Brook Univ., Stony Brook, 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:
- 1224792
- Alternate Identifier(s):
- OSTI ID: 1335403
- Report Number(s):
- BNL-108537-2015-JA; BNL-111845-2016-JA
Journal ID: ISSN 1867-3880; R&D Project: CO-019; KC0302010
- Grant/Contract Number:
- SC00112704; SC0012704; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemCatChem
- Additional Journal Information:
- Journal Volume: 115; Journal Issue: 19; Journal ID: ISSN 1867-3880
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 30 DIRECT ENERGY CONVERSION; potassium; electron polarization; CO2; copper oxide; DFT; STM; Center for Functional Nanomaterials; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Liu, Ping, An, Wei, Stacchiola, Dario, and Xu, Fang. Potassium-induced effect on structure and chemical activity of CuxO/Cu(111) (x≤2) surface: A combined scanning tunneling microscopy and density functional theory study. United States: N. p., 2015.
Web. doi:10.1002/cctc.201500719.
Liu, Ping, An, Wei, Stacchiola, Dario, & Xu, Fang. Potassium-induced effect on structure and chemical activity of CuxO/Cu(111) (x≤2) surface: A combined scanning tunneling microscopy and density functional theory study. United States. https://doi.org/10.1002/cctc.201500719
Liu, Ping, An, Wei, Stacchiola, Dario, and Xu, Fang. Fri .
"Potassium-induced effect on structure and chemical activity of CuxO/Cu(111) (x≤2) surface: A combined scanning tunneling microscopy and density functional theory study". United States. https://doi.org/10.1002/cctc.201500719. https://www.osti.gov/servlets/purl/1224792.
@article{osti_1224792,
title = {Potassium-induced effect on structure and chemical activity of CuxO/Cu(111) (x≤2) surface: A combined scanning tunneling microscopy and density functional theory study},
author = {Liu, Ping and An, Wei and Stacchiola, Dario and Xu, Fang},
abstractNote = {Potassium (K) plays an essential role to promote catalytic reactions in many established industrial catalytic processes. Here in this paper, we report a combined study using STM and DFT to understand the effect of the deposition of K on the atomic and electronic structures as well as chemical activities of CuxO/Cu(111) (x≤2). The DFT calculations show a pseudomorphic growth of K on CuxO/Cu(111) up to 0.19 monolayer (ML) of coverage, in which K binds the surface by a strong ionic interaction with chemisorbed oxygen and relatively weak electrostatic interactions with Cu ions, the lower and upper oxygen atoms on the CuxO rings. The simulated STM pattern based on the DFT results agrees well with the experimental observations. The deposited K has a great impact on the surface electronic structure of CuxO/Cu(111), which induces a significant reduction in the work function and leads to a strong electron polarization on the surface. The promotion of K on the surface binding properties is selective and varies depending on the nature of the adsorbates. According to our results, K has little effect on surface acidity but it enhances the surface basicity significantly. Consequently, the presence of K does not help CO adsorption on CuxO/Cu(111) but is able to accelerate the activation of CO2. Such a promotion depends strongly on the combinations from both geometric and electronic effects. In conclusion, our results highlight the origin of the promoting effect of alkali metals in the design of catalysts for complex reactions.},
doi = {10.1002/cctc.201500719},
journal = {ChemCatChem},
number = 19,
volume = 115,
place = {United States},
year = {Fri Oct 16 00:00:00 EDT 2015},
month = {Fri Oct 16 00:00:00 EDT 2015}
}
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