Poisoning effect of adsorbed CO during CO2 electroreduction on late transition metals

Sneha A. Akhade, Wenjia Luo, Xiaowa Nie, Nicole J. Bernstein, Aravind Asthagiri, Michael John Janik

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Copper cathodes, at sufficiently negative potentials, are selective for hydrocarbon production during the electrochemical reduction of carbon dioxide. Other metals, such as Pt, Fe, Ni and Co, produce low to zero hydrocarbons. We employ density functional theory to examine the coverage of reaction intermediates under CO2 electroreduction conditions. A detailed thermodynamic analysis suggests that a high coverage of adsorbed CO at relevant reduction potentials blocks the metal surface sites for H adsorption, preventing C-H bond formation. The potential-dependent energetics of H adsorption and CO formation are highly sensitive to the surface coverage of the adsorbed species. The formation of surface carbon as a competing adsorption intermediate is also explored at relevant reduction potentials. CO2 electroreduction to hydrocarbons over metals active for the thermal reduction process (Fe, Ni, Co, Pt) would require a H supply for C-H bond formation that is competitive with CO* and C* at the surface.

Original languageEnglish (US)
Pages (from-to)20429-20435
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number38
DOIs
StatePublished - Sep 10 2014

Fingerprint

poisoning
Carbon Monoxide
Transition metals
Hydrocarbons
transition metals
hydrocarbons
Metals
Adsorption
adsorption
Reaction intermediates
reaction intermediates
Carbon Dioxide
metals
metal surfaces
Density functional theory
carbon dioxide
Copper
Cathodes
Carbon
cathodes

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Akhade, Sneha A. ; Luo, Wenjia ; Nie, Xiaowa ; Bernstein, Nicole J. ; Asthagiri, Aravind ; Janik, Michael John. / Poisoning effect of adsorbed CO during CO2 electroreduction on late transition metals. In: Physical Chemistry Chemical Physics. 2014 ; Vol. 16, No. 38. pp. 20429-20435.
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Poisoning effect of adsorbed CO during CO2 electroreduction on late transition metals. / Akhade, Sneha A.; Luo, Wenjia; Nie, Xiaowa; Bernstein, Nicole J.; Asthagiri, Aravind; Janik, Michael John.

In: Physical Chemistry Chemical Physics, Vol. 16, No. 38, 10.09.2014, p. 20429-20435.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Poisoning effect of adsorbed CO during CO2 electroreduction on late transition metals

AU - Akhade, Sneha A.

AU - Luo, Wenjia

AU - Nie, Xiaowa

AU - Bernstein, Nicole J.

AU - Asthagiri, Aravind

AU - Janik, Michael John

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Y1 - 2014/9/10

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AB - Copper cathodes, at sufficiently negative potentials, are selective for hydrocarbon production during the electrochemical reduction of carbon dioxide. Other metals, such as Pt, Fe, Ni and Co, produce low to zero hydrocarbons. We employ density functional theory to examine the coverage of reaction intermediates under CO2 electroreduction conditions. A detailed thermodynamic analysis suggests that a high coverage of adsorbed CO at relevant reduction potentials blocks the metal surface sites for H adsorption, preventing C-H bond formation. The potential-dependent energetics of H adsorption and CO formation are highly sensitive to the surface coverage of the adsorbed species. The formation of surface carbon as a competing adsorption intermediate is also explored at relevant reduction potentials. CO2 electroreduction to hydrocarbons over metals active for the thermal reduction process (Fe, Ni, Co, Pt) would require a H supply for C-H bond formation that is competitive with CO* and C* at the surface.

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