Abstract
Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO 2) on Ni(110). The energetics of surface and subsurface H reacting with surface CO 2 to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO 2 can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid. We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO 2 hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO 2. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.
| Original language | English |
|---|---|
| Pages (from-to) | 1050-1055 |
| Number of pages | 6 |
| Journal | Surface Science |
| Volume | 606 |
| Issue number | 13-14 |
| DOIs | |
| Publication status | Published - Jul 2012 |
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Keywords
- Carbon dioxide
- Carboxyl
- Density functional calculations
- Formate
- Hydrogenation
- Nickel
- Subsurface hydrogen
ASJC Scopus subject areas
- Surfaces and Interfaces
- Condensed Matter Physics
- Materials Chemistry
- Surfaces, Coatings and Films
Cite this
CO 2 hydrogenation to formic acid on Ni(110). / Peng, Guowen; Sibener, S. J.; Schatz, George C; Mavrikakis, Manos.
In: Surface Science, Vol. 606, No. 13-14, 07.2012, p. 1050-1055.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - CO 2 hydrogenation to formic acid on Ni(110)
AU - Peng, Guowen
AU - Sibener, S. J.
AU - Schatz, George C
AU - Mavrikakis, Manos
PY - 2012/7
Y1 - 2012/7
N2 - Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO 2) on Ni(110). The energetics of surface and subsurface H reacting with surface CO 2 to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO 2 can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid. We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO 2 hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO 2. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.
AB - Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO 2) on Ni(110). The energetics of surface and subsurface H reacting with surface CO 2 to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO 2 can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid. We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO 2 hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO 2. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.
KW - Carbon dioxide
KW - Carboxyl
KW - Density functional calculations
KW - Formate
KW - Hydrogenation
KW - Nickel
KW - Subsurface hydrogen
UR - http://www.scopus.com/inward/record.url?scp=84860749532&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84860749532&partnerID=8YFLogxK
U2 - 10.1016/j.susc.2012.02.027
DO - 10.1016/j.susc.2012.02.027
M3 - Article
AN - SCOPUS:84860749532
VL - 606
SP - 1050
EP - 1055
JO - Surface Science
JF - Surface Science
SN - 0039-6028
IS - 13-14
ER -