期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 32, 页码 11347-11354出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja503724j
关键词
-
资金
- U. S. Department of Energy, Office of Basic Energy Sciences [DE-FG02-12ER16354]
We report high catalytic activity of ultrasmall spherical Au-25(SC2H4Ph)(18) and rod-shaped Au-25(PPh3)(10)(C CPh)(5)X-2 (X = Br, Cl) nanoclusters supported on oxides for the semihydrogenation of terminal alkynes into alkenes with >99% conversion of alkynes and similar to 100% selectivity for alkenes. In contrast, internal alkynes cannot be catalyzed by such ligand-on Au-25 catalysts; however, with ligand-off Au-25 catalysts the internal alkynes can undergo semihydrogenation to yield Z-alkenes, similar to conventional gold nanoparticle catalysts. On the basis of the results, a unique activation pathway of terminal alkynes by ligand-on gold nanoclusters is identified, which should follow a deprotonation activation pathway via a R'-C C-[AunLm] (where L represents the protecting ligands on the cluster), in contrast with the activation mechanism on conventional gold nanocatalysts. This new activation mode is supported by observing the incorporation of deprotonated -C CPh as ligands on rod-shaped Au-25(PPh3)(10)(C CPh)(5)X-2 nanodusters under conditions similar to the catalytic reaction and by detecting the R'-C C-[Au-n(SC2H4Ph)(m)] via FT-IR spectroscopy.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据