CO₂ Reduction on Transition Metal (Fe, Co, Ni, and Cu) Surfaces: In Comparison with Homogeneous Catalysis

Description:

Article discussing research on CO₂ reduction on transition metal (Fe, Co, Ni, and Cu) surfaces and a comparison with homogeneous catalysis.

Creator(s):
Creation Date: February 22, 2012
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Total Uses: 193
Past 30 days: 6
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Creator (Author):
Liu, Cong

University of North Texas

Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas

Creator (Author):
Wilson, Angela K.

University of North Texas

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: February 22, 2012
Description:

Article discussing research on CO₂ reduction on transition metal (Fe, Co, Ni, and Cu) surfaces and a comparison with homogeneous catalysis.

Degree:
Department: Chemistry
Note:

Reprinted with permission from the Journal of Physical Chemistry C. Copyright 2012 American Chemistry Society.

Note:

Abstract: Reduction of CO₂ to CO on Fe, Co, Ni, and Cu surfaces has been studied using density functional theory (DFT) methods. Three reaction steps were studied: (a) adsorption of CO₂ (M + CO₂/M) (M = transition metal surface), (b) decomposition of CO₂ (CO₂/M = (CO + O)/M), and (c) desorption of CO ((CO + O)/M = O/M + CO). Binding energies and reaction energies were calculated using the generalized gradient approximation (GGA) via the Perdew-Burke-Ernzerhof (PBE) functional. Calculations show an interesting trend for reaction energies and total reaction barriers, as a function of metal: from Fe to Cu, reactions tend to be less exergonic; the metals earlier in the 3d series have lower total barriers for CO₂ reduction. However, "overbinding" of CO₂ on Fe causes a thermodynamic sink on the reaction coordinate, and Co and Ni are more favorable in terms of a smaller fluctuation in reaction energies/barriers for these elementary catalytic steps. A Brønsted-Evans-Polanyi (BEP) relationship was analyzed for C-O bond scission of CO₂ on the metal surfaces. Heterogeneous catalysis is also compared with the homogeneous models using transition metal β-diketiminato complexes, showing that both heterogeneous and homogeneous catalysis of CO₂ reduction display the same energetic trend as a function of metal.

Physical Description:

8 p.

Language(s):
Subject(s):
Keyword(s): transition metals | density functional theory | Perdew-Burke-Ernzerhof | heterogeneous catalysis
Source: Journal of Physical Chemistry C, 2012, Washington DC: American Chemical Society, pp. 5681-5688
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/jp210480c
  • ARK: ark:/67531/metadc107801
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Journal of Physical Chemistry C
Volume: 116
Issue: 9
Page Start: 5681
Page End: 5688
Peer Reviewed: Yes