Citation: LI Jun-Nan, PU Min, HE Shu-Heng, HE Jing, EVANS David G.. Reaction Mechanism of Acetylene Hydrogenation Catalyzed by Pd₈ Cluster[J]. Acta Physico-Chimica Sinica, ;2011, 27(04): 793-800. doi: 10.3866/PKU.WHXB20110332 shu

Reaction Mechanism of Acetylene Hydrogenation Catalyzed by Pd₈ Cluster

1.
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China

Received Date: 19 October 2010
Available Online: 17 February 2011
Fund Project: 国家自然科学基金(20531010, 20773009) (20531010, 20773009)国家重点基础研究发展计划(973) (2009CB939802)资助项目 (973) (2009CB939802)

The mechanism of acetylene hydrogenation catalyzed by Pd₈ cluster was investigated by density functional theory (DFT) method at B3PW91/GEN level. The calculation results showed that H₂ dissociated into H atoms wherever it adsorbed and the H atoms then adsorbed onto the surface of the Pd₈ cluster. The dissociation of H₂ is necessary for the hydrogenation of acetylene to ethane catalyzed by the Pd₈ cluster. The mechanism of acetylene hydrogenation is dependent on two isomers: acetylene and vinylidene on the Pd₈ cluster (Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂). The two pathways follow a multistep and successive process to complete the hydrogenation of acetylene. However, a difference exists between Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂. For the Pd₈(2H)－CH＝CH pathway, dissociated H atoms add to the C atom of acetylene on the Pd₈ cluster in different steps until they produce ethane. The Pd₈(2H)－CH＝CH₂ pathway is complex and proceeds by two different transition states to create ethylidyne, and then H atoms add to the C atom until hydrogenation ceases. Many valuable C₂ organic intermediate compounds are produced during the process and some of them transform by proton translocation, which connects the Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂ pathways.
- Density functional theory,
- Pd₈ cluster,
- Acetylene hydrogenation,
- Ethylene,
- Reaction mechanism
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沈阳化工大学材料科学与工程学院沈阳 110142

Reaction Mechanism of Acetylene Hydrogenation Catalyzed by Pd8 Cluster

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通讯作者: 陈斌, bchen63@163.com

Reaction Mechanism of Acetylene Hydrogenation Catalyzed by Pd₈ Cluster