Res. Chem. Intermed.
, Vol. 29, No. 4, pp. 417–428 (2003)
Also available online - www.vsppub.com
Interactions of water and methanol with a mixture of
copper and zinc metals: a theoretical ab initio study
N. U. ZHANPEISOV
and A. MIYAMOTO
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University,
1-1 Gakuen-cho, Sakai, Osaka 599-8531, Japan
Department of Materials Chemistry, Tohoku University, Aoba-yama 07, Sendai, 980-8579, Japan
Received 17 December 2002; accepted 4 March 2003
cluster quantum chemical calculations at the Hartree–Fock and second-order
Møller–Plesset perturbation theory levels were carried out to mimic the interactions of water and
methanol with a mixture of Cu and Zn metals. It was shown that both molecular and dissociative
adsorption of methanol on a mixture of Cu and Zn metal catalyst are preferred over the corresponding
adsorptions of water. Estimated transition-state structures for dissociation of methanol into CH
lie about 9.0 and 22.0 kcal/mol higher compared to the dissociated (forward reaction) and
molecular adsorption (reverse reaction) complexes, respectively. Based on distinct radicals’ bond
energies with the active sites of the catalyst considered, it is suggested that hydrogen molecules could
be formed through a chain of homogeneous reactions of methyl radicals released into the gas phase
with the water and/ or methanol molecules.
; DFT; methanol; water; Cu and Zn metal alloys; hydrogen production.
Selective catalytic reduction of nitrogen oxides by hydrocarbons and/or ammonia
is one of the fascinating chemical processes to decrease or remove NO
exhaust gases of diesel and other lean-burn automobile engines [1– 5]. This is ex-
tremely important with regard to the greenhouse effect and global air pollution con-
trol as well as with the development of environmentally friendly technologies [3– 9].
Nowadays, there is growing interest to solve the problem, especially through nd-
ing more effective and cheap chemicals to replace commonly used gasoline. The
use of methanol instead of gasoline might be one of the promising solutions. The
idea is based on the use of diluted solutions of methanol with water to produce
molecular hydrogen where a possibility arises to combine the two main reactions
To whom correspondence should be addressed.