Structuring hybrid palladium nanoparticles in metallic monolithic reactors for continuous-flow three-phase alkyne hydrogenation

Palladium nanoparticles modified with the hexadecyl-2-hydroxyethyl-dimethylammonium dihydrogen phosphate (HHDMA) ligand have been stabilised within the microchannels of a metallic monolith coated with a high-surface area γ-Alumina layer. The stainless steel skeleton of the monolith was 3D printed by stereolithography. The washcoating protocol has been optimised in order to maximise the γ-Alumina loading without blocking the microchannels. A battery of techniques has been applied to characterise the properties and three-dimensional organisation of the phases within the monolithic reactor from the macro-to the nanoscale including N2 sorption, X-ray diffraction, thermogravimetric analysis, nuclear magnetic resonance and infrared spectroscopies, X-ray tomography, and optical or electron microscopies. Evaluation of the catalyst performance in the flow hydrogenation of acetylenic compounds of different size and functionality demonstrates the high efficiency and stability of the structured catalyst. Particularly, the monolithic reactor retains the intrinsic selective character of the hybrid palladium nanoparticles, even at high temperatures and pressures (T > 343 K and P > 5 bar). This is attributed to the improved isothermicity of the catalyst bed, deriving from the high thermal conductivity of the metallic skeleton of the monolith. Overall, the work provides a general route to prepare monolithic reactors based on Pd-HHDMA nanoparticles, bridging the gap between hybrid nanomaterial and reactor engineering.