화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.115, No.37, 10245-10250, 2011
Experimental and Theoretical Study of Hydrogen Atom Abstraction from n-Butane by Lanthanum Oxide Cluster Anions
Lanthanum oxide cluster anions are prepared by laser ablation and reacted with n-C(4)H(10) in a fast flow reactor. A time-of-flight mass spectrometer is used to detect the cluster distribution before and after the reactions. (La(2)O(3))(m=1-3)OH(-) and La(3)O(7)H(-) are observed as products, which suggests the occurrence of hydrogen atom abstraction reactions: (La(2)O(3))(m=1-3)O(-) + n-C(4)H(10) -> (La(2)O(3))(m=1-3)OH(-) + C(4)H(9) and La(3)O(7)(-) + n-C(4)H(10) -> La(3)O(7)H(-) + C(4)H(9) . Density functional theory (DFT) calculations are performed to study the structures and bonding properties of La(2)O(4)(-), La(3)O(7)(-), and La(4)O(7)(-) dusters. The calculated results show that each of La(2)O(4)(-) and La(4)O(7)(-) contains one oxygen-centered radical (O(-center dot)) which is responsible for the high reactivity toward n-C(4)H(10). La(3)O(7)(-) contains one oxygen-centered radical (O(-center dot)) and one superoxide unit (O(2)(-center dot)), and the O(-center dot) is responsible for its high reactivity toward n-C(4)H(10). The O(-center dot) and O(2)(-center dot) can be considered to be generated by the adsorption of an O(2) molecule onto the singlet La(3)O(5)(-) with electron transfer from a terminally bonded oxygen ion (O(2-)) to the O(2). This may help us understand the mechanism of the formation of O(-center dot) and O(2)(-center dot) radicals in lanthanum oxide systems. The reaction mechanisms of La(2)O(4)(-) + n-C(4)H(10) and La(3)O(7)(-) + n-C(4)H(10) are also studied by the DFT calculations, and the calculated results are in good agreement with the experimental observations.