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Atomic and Molecular Adsorption on Cu(111)

Journal Article · · Topics in Catalysis
 [1];  [2];  [2];  [2]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States); University of Wisconsin-Madison Department of Chemical and Biological Engineering
  2. Univ. of Wisconsin-Madison, Madison, WI (United States)
+ Show Author Affiliations
Here, due to the wide use of copper-based catalysts in industrial chemical processes, fundamental understanding of the interactions between copper surfaces and various reaction intermediates is highly desired. Here, we performed periodic, self-consistent density functional theory (DFT-GGA) calculations to study the adsorption of five atomic species (H, C, N, O, and S), seven molecular species (NH3, CH4, N2, CO, HCN, NO, and HCOOH), and 13 molecular fragments (CH, CH2, CH3, NH, NH2, OH, CN, COH, HCO, COOH, HCOO, NOH, and HNO) on the Cu(111) surface at a coverage of 0.25 monolayer. The preferred binding site, binding energy, and the corresponding surface deformation energy of each species were determined, as well as the estimated diffusion barrier and diffusion pathway. The binding strengths calculated using the PW91 functional decreased in the following order: CH > C > O > S > CN > NH > N > CH2 > OH > HCOO > COH > H > NH2 > NOH > COOH > HNO > HCO > CH3 > NO > CO > NH3 > HCOOH. No stable binding structures were observed for N2, HCN, and CH4. The adsorbate–surface and intramolecular vibrational modes of all the adsorbates at their preferred binding sites were deternined. Using the calculated adsorption energetics, potential energy surfaces were constructed for the direct decomposition of CO, CO2, NO, N2, NH3, and CH4 and the hydrogen-assisted decomposition of CO, CO2, and NO.
Research Organization:
Univ. of Wisconsin-Madison, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Contributing Organization:
National Energy Research Scientific Computing Center (NERSC); and the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility at Pacific Northwest National Laboratory (PNNL); the Center for Nanoscale Materials (CNM) at Argonne National Laboratory (ANL)
Grant/Contract Number:
FG02-05ER15731
OSTI ID:
1440993
Journal Information:
Topics in Catalysis, Journal Name: Topics in Catalysis Journal Issue: 7-8 Vol. June 2018; ISSN 1022-5528; ISSN 1572-9028
Publisher:
SpringerCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

DFT and microkinetic investigation of methanol synthesis via CO 2 hydrogenation on Ni(111)-based surfaces journal January 2019
Electronic effects due to organic linker-metal surface interactions: implications on screening of MOF-encapsulated catalysts journal January 2020
Van der Waals density functional study of formic acid adsorption and decomposition on Cu(111) journal April 2019
The roles of step-site and zinc in surface chemistry of formic acid on clean and Zn-modified Cu(111) and Cu(997) surfaces studied by HR-XPS, TPD, and IRAS journal January 2020

Figures / Tables (13)

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Figure 5(p. 21)figure Figure 5

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Adsorption
Catalysis
Copper
Density functional theory
Thermochemistry