Theoretical Investigation on Structures,Stabilities,and Hydrolysis Reactions of Small RuO_(2)Nanoclusters  

作　　者：Hao Dong Zhonghua Zan Xin Zhou 

机构地区：[1]Institute of Chemistry for Functionalized Materials,School of Chemistry and Chemical Engineering,Liaoning Normal University,Dalian,Liaoning 116029,China [2]State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian National Laboratory for Clean Energy,Dalian,Liaoning 116023,China

出　　处：《Chinese Journal of Chemistry》2014年第6期527-537,共11页中国化学（英文版）

基　　金：Dr.Dong gratefully acknowledges the funding sup-port by National Natural Science Foundation of China under Grant 21303079 and the financial support from Liaoning Normal University;Dr.Zhou appreciates the funding support by National Natural Science Founda-tion of China under Grant 21003115.

摘　　要：The geometric structures and relative stabilities of both neutral and ionic(RuO_(2))_(n)(n=1-5)nanoclusters have been systematically investigated using density functional theory calculations.Differently from the crystal structure,ruthenium tends to adopt a 4-fold coordination with either terminal Ru=O or bridging Ru-O bonds in gas phase clusters.Our calculations show that three-dimensional compact structures are more preferred with the increase of the cluster size.For the low-lying(RuO_(2))_(n)clusters,the cluster formation energy per RuO_(2)unit and the electron af-finity are found to increase whereas the ionization potential is computed to decrease with the cluster size.Based on the optimized lower-energy structures of neutral and cationic(RuO_(2))_(n)(n=1-5),the hydrolysis reactions of these clusters with water molecules have been further explored.The calculated results indicate that the adsorption of wa-ter molecules to the cationic species is much easier than the neutral ones.The overall hydrolysis reaction energies are more exothermic for the cationic clusters than for the neutral clusters.Our calculations indicate that thermody-namically,H_(2)O can be more easily split on the cationic ruthenium oxide clusters than on the neutral clusters.

关 键 词：density functional calculations ruthenium oxide clusters water oxidation PHOTOCATALYSIS cocatalytsts 

分 类 号：O64[理学—物理化学]