ThO+/0/-2不同电荷态对N2O氧化CO反应的影响

本文采用密度泛函理论，对ThO^+/0/-₂团簇参与CO与N₂O间氧化还原反应(CO+N₂O→CO₂+N₂)的机理展开研究，探讨钍氧团簇所带的电荷对该反应的影响.研究表明：ThO^+/0/-₂在反应中主要起传输氧原子的作用，其中ThO⁺₂与CO的反应以及ThO^+/0/-与N₂O的反应都为热力学上的放热反应，而ThO^0/-₂与CO的反应为热力学上的吸热反应.随着电荷态的改变，ThO^+/0/-₂与CO反应的总能垒(E_b)与总驱动力(-ΔG)有较大差异.因此，通过改变ThO₂的电荷态能调节其对CO/N₂O反应的催化活性，综合考虑，ThO⁺₂对...

Oxidation Reactions of CO by N2O on ThO2+/0/- Clusters: The Effect of Charge States of ThO2

Density functional theory (DFT) calculations at the B3LYP level are performed to investigate the redox reactions between CO and N2O in which ThO2+/0/- clusters participate. The reaction mechanisms are illustrated and the impacts of the charge states of ThO2+/0/- on the above reactions are evaluated as well. Our results show that ThO2+/0/- play the role of transporting O atom in the CO/N2O redox reaction. The reaction of ThO2+ with CO is exothermic, while those of ThO2-/0 with CO are endothermic. As for the reactions of ThO+/0/- with N2O, they are all exothermic. With the change of the charge state, the energy barriers (Eb) and the driving forces (-∆G) of the overall reactions show big differences for ThO2+, ThO2 and ThO2- reacting with CO, respectively. Therefore, by changing the charge state of ThO2, its redox ability can be regulated. In summary, the positively charged ThO2+ cluster shows the highest catalytic activity in the above CO/N2O redox reaction.