Tuning the composition of metallic nanoparticles for catalytic applications

Sammanfattning: Industries’ interest in nanomaterials is tremendous and catalysis is one of their applications. Catalysts allow reactions to occur under milder conditions, avoiding committing excessive heat or pressure to foster reactions. The discovery of Frustrated Lewis Pairs (FLP) in 2006 led to a new concept of homogeneous catalysis: metal-free acids and bases preventing from forming an Lewis adduct because their bulkiness create an active clamp that is able to cleave dihydrogen and other small molecules at room temperature. Transferring the FLP concept to the “nano”-world which is more relevant for industrial applications, requires well-designed nanoparticles and rationalization of their interaction with ligands aiming at forming a FLP between nanoparticles and ligands. The following project conducted at LCMCP (Laboratoire de Chimie de la Matière Condensée de Paris) under the supervision of Sophie Carenco aimed at studying the insertion of phosphorus in metallic nanoparticles in order to tune their catalytic activity and demonstrate Frustrated-Lewis Pair catalytic behaviours. To that end, copper nanoparticles and bimetallic core-shell nickel-cobalt nanoparticles were synthesized in colloidal solution. The phosphidation of both nanoparticles was investigated with trioctylphosphine (TOP) as the phosphorous source. Nanoparticles were characterized by X-Ray Diffraction, Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy. Starting from the failure to reproduce a published procedure of copper phosphide nanoparticles synthesis, conditions of the reaction and the washing procedure were successively improved aiming the obtention of copper phosphide nanoparticles. The one-pot synthesis with hot-injection of TOP at the second step (320°C, 1h), allowed to isolate copper phosphide nanoparticles but a longer reaction time did not result in enhanced phosphorus doping. Further work would need to examine the reproducibility problems faced and investigate harsher reaction conditions (eg. higher temperature). Cu3P nanoparticles would be interesting to test as catalysts for hydrosilylation of benzaldehyde or CO2, a model reaction for CO2 hydrogenation. The synthesis of core-shell nickel-cobalt nanoparticles has been previously rationalized by Sophie Carenco’s team. Phosphidation was attempted from this optimized procedure. We started with harsh conditions (> 250°C, > 1h30) which caused reconstruction of the nanoparticles after leaching of the cobalt shell. In such conditions, the core-shell structure is not retained and a NiCoP alloy is obtained. Milder conditions allowed to retain the structure but further studies are required to characterize and locate the phosphorus insertion in the core-shell nanoparticles. NiCoP alloy and phosphidized core-shell Ni@Co will be of great interest to apply in catalysis for water splitting and hydrogenation of nitriles, respectively.