PNNL

Abstract

The activation of H2 on NaY-encapsulated Mo sulfide clusters is significantly influenced by the presence of Ni at ion exchange positions. Ni was incorporated by partially ion exchanging the NaY zeolite with Ni2+ cations. Mo(CO)6 vapors were subsequently deposited on the ion exchanged NiNaY zeolites, followed by sulfidation in 10 vol.% H2S/H2 at 673 K, leading to the formation of dimeric Mo2S4 clusters connected to Ni2+ via bridging S atoms. In contrast to the monometallic Mo sulfide clusters, which stabilize adsorbed hydrogen primarily as hydrides on Mo atoms, the bimetallic Ni-Mo sulfide clusters bind hydrogen also as sulfhydryl groups on the bridging sulfur atoms. The formation of sulfhydryl groups in Ni-Mo sulfide clusters is attributed to the lower electron density on the cluster due to coordination with more electronegative Ni2+. The ethene hydrogenation rate was significantly higher on the bimetallic Ni-Mo sulfide catalysts, compared to monometallic Mo sulfide catalysts, because the stabilization of atomic hydrogen as sulfhydryl groups opens a new hydrogenation path-way.