Surface Oxygen‐Assisted Pd Nanoparticle Catalysis for Selective Oxidation of Silanes to Silanols

Abstract

Just add O(2): Based on the fact that an oxygen-adsorbed Pd metal surface shows higher reactivity for water dissociation than a clean Pd surface, carbon-supported Pd nanoparticles (NPs) with surface oxygen atoms were developed as a highly effective and reusable heterogeneous catalyst for selective oxidation of silanes to silanols with water as a green oxidant (see figure).

On-demand Hydrogen Production from Organosilanes at Ambient Temperature Using Heterogeneous Gold Catalysts

“…In addition, the use of heterogeneous catalysts should allow easy separation from organosilane, leading to on/off-switching of H 2 -production. Several heterogeneous catalysts for the hydrolytic oxidation of organosilanes have been reported28293031323334353637. However, these catalysts were developed for the synthesis of organosilanols, and no attention has been paid for the utilization of heterogeneous catalysts for H 2 -production through hydrolytic oxidation of inexpensive organosilanes such as PMHS and TMDS.…”

Heterogeneous nickel catalyst for selective hydration of silanes to silanols

“…Under high substrate/catalyst ratio (10,000) conditions, 5 mmol of the silane 1a (entry 5) was selectively oxidized to the corresponding silanol in 93% yield after 24 h at 80 • C, corresponding to TON of 9300 and TOF of 387 h −1 (based on total Ni content). [21], and AuNPore (100 h −1 ) [22], though it is lower than those of Pd/C (TOF 20,000 h −1 ) [19] and AuCNT (18,000 h −1 ) [23]. Other aliphatic silanes (Pr 3 SiH and Bu 3 SiH) were also selectively converted to the corresponding silanols (entries 6 and 7).…”

“…Among various preparation methods of silanols, recent attention has been focused on the oxidation of organosilanes with water under neutral conditions by noble-metal catalysts. Homogeneous (Ir [8], Re [9,10], Rh [11], Ru [12,13], Pt [14], Ag [15]) and heterogeneous (Ru [16,17], Ag [18], Pd [19,20], Au [21][22][23]) noble-metal catalysts were developed. Homogeneous [24] and heterogeneous [20,25] catalysts based on Cu or Ni were also reported, but their activity was lower than the noble-metal catalysts.…”

Chlorine‐Free Catalytic Formation of Silsesquioxanes with Si‐OH and Si‐OR Functional Groups

“…The catalytic methods for Si‐H oxidation occurring in the presence of transition metals have gained much attention . These procedures use homogeneous catalysis based on both early and late TM compounds such as Ru, Rh, Ir, Re, Pd, Pt, Hf, Co, Ti, Cr, Cu and Ag salts and complexes . Also, a report on the Te organometallic compounds is known .…”