Bismuth−Palladium Heterometallic Carboxylate as a Single-Source Precursor for the Carbon-Supported Pd−Bi/C Catalysts

详细信息    查看全文

• 作者：Bo Li ; Haitao Zhang ; Lan Huynh ; Chantal Diverchy ; Sophie Hermans ; Michel Devillers ; Evgeny V. Dikarev
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：July 6, 2009
• 年：2009
• 卷：48
• 期：13
• 页码：6152-6158
• 全文大小：827K
• 年卷期：v.48,no.13(July 6, 2009)
• ISSN：1520-510X

文摘

The heterometallic complex [Bi₂Pd₂(O₂CCF₃)₁₀(HO₂CCF₃)₂] (1) was obtained by the solid state reaction of Bi^III trifluoroacetate/trifluoroacetic acid adduct with unsolvated trinuclear Pd^II trifluoroacetate. The crystal structure of 1 consists of discrete tetranuclear molecules, in which two paddlewheel [BiPd(O₂CCF₃)₄] units are connected by two chelating-bridging trifluoroacetate ligands through bismuth ends. There are no metal−metal bonds in the tetrameric structure of 1, since both Bi···Pd (3.0843(4) Å) and Bi···Bi (4.5074(4) Å) distances are too long to be considered as bonding interactions. A study of the solution behavior revealed that not only the coordinated trifluoroacetic acid in 1 can be effectively replaced by other donor solvent molecules but also the tetranuclear complex can be cleaved in solution into discrete dinuclear Bi−Pd species. Complex 1 was used as precursor for the preparation of a bimetallic Pd−Bi carbon-supported catalyst. The preparation procedure included the modification of the carbon support to increase the number of oxygenated functions at its surface followed by grafting complex 1 via ligand exchange for surface carboxylates and activating thermally. The resulting catalyst, consisting of small supported metallic particles, was found to be more active than the reference materials prepared from multisource homometallic Pd and Bi precursors.