Reactions of D₂ with 1,4‐Bis(diphenylphosphino) butane‐Stabilized Metal Nanoparticles‐A Combined Gas‐phase NMR, GC‐MS and Solid‐state NMR Study

Abstract

The reactions of three metal nanoparticle (MNP) systems Ru/ dppb, RuPt/dppb, Pt/dppb (dppb = 1,4-bis(diphenylphosphino)butane) with gaseous D 2 at room temperature and different gas pressures have been studied using 1 H gas phase NMR, GC-MS and solid state 13 C and 31 P MAS NMR. The main product is gaseous HD arising from the reaction of D 2 with surface hydrogen sites created during the synthesis of the nanoparticles. In a side reaction, some of the dppb ligands are decomposed producing surface phosphorus species and gaseous partially deuterated butane and cyclohexane. These findings are fundamental for detailed studies of the reaction kinetics of these particles towards H 2 or D 2 gas.

Chemoselective H/D exchange catalyzed by nickel nanoparticles stabilized by N-heterocyclic carbene ligands

“…In addition, upon adjusting the nature of the stabilizing ligands at the surface of the NPs, the reactivity, solubility or selectivity of the system can be easily tuned, which constitutes an advantage over the classical heterogeneous catalysts. MNPs are well-known catalysts for the H-H and D-D activation [19][20][21][22] and, therefore, they have been widely employed in catalytic hydrogenation. 23 A more recent development of MNPs reactivity is C-H activation in mild conditions, which may present several potential applications.…”

Catalysis with Colloidal Ruthenium Nanoparticles

“…The surface hydrides can be displaced by coordination of CO at the surface. NMR methods, in particular solid-state 2 H NMR, evidenced H–D exchange between Ru NPs surface and ligand sites: incorporation of 2 H atoms in the alkylchains of HDA used as capping ligand was observed, as the result of a C–H activation phenomenon. , This was further exploited in order to perform the deuteration of different substrates (vide infra). Using 13 CO as a probe molecule and IR (Infrared) and MAS NMR (magic angle spinning nuclear magnetic resonance) techniques provided indirect information on location and mobility of ligands at metal surface and helped to understand the surface properties and catalytic reactivity of NPs .…”

σ-H–H, σ-C–H, and σ-Si–H Bond Activation Catalyzed by Metal Nanoparticles

“…Rothermel et al have extended the characterization of surface hydrides coordinated to monometallic and bimetal NPs. 67 Three different systems were prepared in this work: Ru/dppb, Pt/dppb, and RuPt/dppb (dppb = 1,4-bis(diphenylphosphino)butane). After treatment with D 2 , the authors carried out the characterization of the products via gas-phase NMR, GC-MS, and 13 C and 31 P solid-state NMR.…”

“…Rothermel et al have extended the characterization of surface hydrides coordinated to monometallic and bimetal NPs . Three different systems were prepared in this work: Ru/dppb, Pt/dppb, and RuPt/dppb (dppb = 1,4-bis­(diphenylphosphino)­butane).…”