| Description: | This article discusses CO₂ reduction on transition metal (Fe, Co, Ni, and Cu) surfaces. 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, adn 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. |
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| Creator(s): | |
| Creation Date: | February 22, 2012 |
| Partner(s): |
UNT College of Arts and Sciences
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| Collection(s): |
UNT Scholarly Works
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| Usage: |
Total Uses: 90
Past 30 days: 19
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| Creator (Author): |
Liu, Cong
University of North Texas |
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| Creator (Author): |
Cundari, Thomas R., 1964-
University of North Texas |
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| Creator (Author): |
Wilson, Angela K.
University of North Texas |
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| Publisher Info: |
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
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| Date(s): |
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| Description: | This article discusses CO₂ reduction on transition metal (Fe, Co, Ni, and Cu) surfaces. 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, adn 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. |
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| Degree: |
Department:
Chemistry
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| Note: |
Reprinted with permission from the Journal of Physical Chemistry C. Copyright 2012 American Chemistry Society. |
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| Physical Description: |
8 p. |
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| 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
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| Collection: |
UNT Scholarly Works
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| Resource Type: | Article | |
| Format: | Text | |
| Rights: |
Access:
Public
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| Citation: |
Publication Title: Journal of Physical Chemistry C
Volume: 116
Issue: 9
Page Start: 5681
Page End: 5688
Peer Reviewed: Yes
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