期刊
CHEMCATCHEM
卷 5, 期 12, 页码 3750-3759出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201300569
关键词
B5 sites; H-2 activation; hydrogenation; mechanistic studies; nanoparticles; olefins; silver
资金
- ETH Zurich
- Ministerio de Economia y Competitividad (Spain) [CTQ2012-33826]
- ICIQ Foundation
The gas-phase partial hydrogenation of propyne was investigated over supported Ag nanoparticles (2-20nm in diameter) prepared by using different deposition methods, activation conditions, loadings, and carriers. The excellent selectivities to propene attained over the catalysts, exceeding 90%, are independent of the particle size but the activity is maximal over approximately 4.5nm Ag particles. Certain kinetic fingerprints of Ag, such as the positive dependence on the alkyne pressure, the relatively low reaction order in H-2, and the low apparent activation energy, deviate from those of conventional hydrogenation metals such as Pd and Ni, questioning the applicability of the classical Horiuti-Polanyi scheme. Periodic dispersion-corrected density functional theory (DFT-D) calculations and microkinetic analysis demonstrate the occurrence of an associative mechanism, which features the activation of H-2 on the adsorbed propyne at structural step sites. By using the atomistic Wulff model, the number of B5 sites available on the Ag nanoparticles was estimated to be maximal in the size range of 3.5-4.7nm. The rate of propene production correlates with the density of B5 sites, which suggests that the latter are potential active centers for the reaction. This alternative pathway broadens the mechanistic diversity of hydrogenation reactions over metal surfaces and opens new directions for understanding metals that do not readily activate H-2.
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