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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

Journal Article · · ChemCatChem
 [1];  [2];  [1];  [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Shanghai Univ. of Engineering Science, Shanghai (China)
  3. Stony Brook Univ., Stony Brook, NY (United States)
+ Show Author Affiliations

Potassium (K) plays an essential role in promoting catalytic reaction in many established industrial catalytic processes. Here, we report a combined study using scanning tunneling microscopy (STM) and density functional theory (DFT) in understanding the effect of depositing K on the atomic and electronic structures as well as chemical activities of CuxO/Cu(111) (x≤2). The DFT calculations observe a pseudomorphic growth of K on CuxO/Cu(111) up to 0.19 monolayer (ML) of coverage, where K binds the surface via strong ionic interaction with chemisorbed oxygen and the relatively weak electrostatic interactions with copper ions, lower and upper oxygen on the CuxO rings. The simulated STM pattern based on the DFT results agrees well with the experimental observations. The deposited K displays great impact on the surface electronic structure of CuxO/Cu(111), which induces significant reduction in work function and leads to a strong electron polarization on the surface. The promotion of K on the surface binding properties is selective. It varies depending on the nature of adsorbates. According to our results, K has little effect on surface acidity, while it enhances the surface basicity significantly. As a consequence, the presence of K does not help for CO adsorption on CuxO/Cu(111), but being able to accelerate the activation of CO2. Thus, such promotion strongly depends on the combinations from both geometric and electronic effects. Our results highlight the origin of promoting effect of alkalis in the design of catalysts for the complex reactions.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI ID:
1224792
Alternate ID(s):
OSTI ID: 1335403
Report Number(s):
BNL--108537-2015-JA; KC0302010
Journal Information:
ChemCatChem, Journal Name: ChemCatChem Journal Issue: 19 Vol. 115; ISSN 1867-3880
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

DFT insight into the effect of potassium on the adsorption, activation and dissociation of CO 2 over Fe-based catalysts journal January 2018
Activation of CO 2 at the electrode–electrolyte interface by a co-adsorbed cation and an electric field journal January 2019
Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction journal August 2019

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Related Subjects

30 DIRECT ENERGY CONVERSION
CO2
Center for Functional Nanomaterials
DFT
STM
copper oxide
electron polarization
potassium