Abstract
A study using ab initio MO calculations and frontier orbital theory has been performed to investigate the effect of substitutional boron on the electronic structure and reactivity of eight-ring carbon model structures. This theoretical analysis confirmed that boron substitution in the carbon lattice can result in two opposite effects on carbon oxidation: catalysis and inhibition. Boron substitution was found to decrease the global cluster stability and to affect the local reactivity of its edge sites. For a zigzag cluster, the reactivity of carbon active sites may be increased or decreased by boron substitution and the exact effect appears to be dependent on substituent position: in general, the reactivity of unsaturated edge sites decreases, but substitution at certain basal-plane sites may increase the reactivity of some active sites which in turn suggests a catalytic effect. For an armchair cluster, boron substitution increases the reactivity of one or more armchair edge sites. Single atom substitution in the zigzag cluster may result in thermodynamically favorable or unfavorable O 2 chemisorption; the exact effect was found to be site-dependent. It also increases the energy barrier for CO desorption. Such an intriguing dual effect provides an explanation for the experimentally observed conflicting effects of boron doping in carbon oxidation.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 9180-9187 |
| Number of pages | 8 |
| Journal | Journal of Physical Chemistry A |
| Volume | 108 |
| Issue number | 42 |
| DOIs | |
| State | Published - Oct 21 2004 |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
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Ab initio molecular orbital study on the electronic structures and reactivity of boron-substituted carbon. / Wu, Xianxian; Radovic, Ljubisa R.
In: Journal of Physical Chemistry A, Vol. 108, No. 42, 21.10.2004, p. 9180-9187.Research output: Contribution to journal › Article
TY - JOUR
T1 - Ab initio molecular orbital study on the electronic structures and reactivity of boron-substituted carbon
AU - Wu, Xianxian
AU - Radovic, Ljubisa R.
PY - 2004/10/21
Y1 - 2004/10/21
N2 - A study using ab initio MO calculations and frontier orbital theory has been performed to investigate the effect of substitutional boron on the electronic structure and reactivity of eight-ring carbon model structures. This theoretical analysis confirmed that boron substitution in the carbon lattice can result in two opposite effects on carbon oxidation: catalysis and inhibition. Boron substitution was found to decrease the global cluster stability and to affect the local reactivity of its edge sites. For a zigzag cluster, the reactivity of carbon active sites may be increased or decreased by boron substitution and the exact effect appears to be dependent on substituent position: in general, the reactivity of unsaturated edge sites decreases, but substitution at certain basal-plane sites may increase the reactivity of some active sites which in turn suggests a catalytic effect. For an armchair cluster, boron substitution increases the reactivity of one or more armchair edge sites. Single atom substitution in the zigzag cluster may result in thermodynamically favorable or unfavorable O 2 chemisorption; the exact effect was found to be site-dependent. It also increases the energy barrier for CO desorption. Such an intriguing dual effect provides an explanation for the experimentally observed conflicting effects of boron doping in carbon oxidation.
AB - A study using ab initio MO calculations and frontier orbital theory has been performed to investigate the effect of substitutional boron on the electronic structure and reactivity of eight-ring carbon model structures. This theoretical analysis confirmed that boron substitution in the carbon lattice can result in two opposite effects on carbon oxidation: catalysis and inhibition. Boron substitution was found to decrease the global cluster stability and to affect the local reactivity of its edge sites. For a zigzag cluster, the reactivity of carbon active sites may be increased or decreased by boron substitution and the exact effect appears to be dependent on substituent position: in general, the reactivity of unsaturated edge sites decreases, but substitution at certain basal-plane sites may increase the reactivity of some active sites which in turn suggests a catalytic effect. For an armchair cluster, boron substitution increases the reactivity of one or more armchair edge sites. Single atom substitution in the zigzag cluster may result in thermodynamically favorable or unfavorable O 2 chemisorption; the exact effect was found to be site-dependent. It also increases the energy barrier for CO desorption. Such an intriguing dual effect provides an explanation for the experimentally observed conflicting effects of boron doping in carbon oxidation.
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U2 - 10.1021/jp048212w
DO - 10.1021/jp048212w
M3 - Article
AN - SCOPUS:7544225843
VL - 108
SP - 9180
EP - 9187
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 42
ER -