LAUSR

Mononuclear Ru halogen carbonyl complex was the exclusive to catalyze the water-gas reaction (WGR) according to Ken-ichi Tominaga et al. Density functional theory (DFT) is employed to study the water-gas shift reaction (WGSR) in basic solution for [RuCl3(CO)3]−. Four different mechanistic pathways have been considered. The calculations indicate that formic acid mechanism to be competitive. The energetic span model (ESM) proposed by Shaik et al. has been applied to reveal the kinetic behavior of the four catalytic cycles. The one with the highest efficiency usually gives the highest TOF. The formic acid mechanism exhibits high catalytic activity towards water gas shift reaction due to the highest value of the calculated turnover frequency (1.89 × 10–14 s–1), which is higher than the value of TOF (1.74 × 10–16 s–1, Ru(CO)5; 1.88 × 10–15 s–1, Fe(CO)5). It turned out that [Ru(CO)3Cl3]– is a promising candidate for an improved WGSR catalyst and a better catalyst for the industrially important reaction.