Ligand-free Ni nanocluster formation at atmospheric pressure via rapid quenching in a microplasma process

The production of metal nanoclusters composed of less than 10(3) atoms is important for applications in energy conversion and medicine, and for fundamental studies of nanomaterial nucleation and growth. Unfortunately, existing synthesis methods do not enable adequate control of cluster formation, particularly at atmospheric pressure wherein formation typically occurs on sub-millisecond timescales. Here, we demonstrate that ligand-free, unagglomerated nickel nanoclusters can be continuously synthesized at atmospheric pressure via the decomposition of bis(cyclopentadienyl)nickel(II) (nickelocene) in a spatially-confined microplasma process that rapidly quenches particle growth and agglomeration. The clusters were measured on line by ion mobility spectrometry (IMS) and further analyzed by atomic force microscopy (AFM). Our results reveal that stable clusters with spherical equivalent mean diameters below 10 Åare produced, and by controlling the nickelocene concentration, the mean diameter can be tuned up to ∼50 Å. Although diameter is often the sole metric used in nanocluster and nanoparticle characterization, to infer the number of atoms in AFM and IMS detected clusters, we compare measured AFM heights and IMS inferred collision cross sections to theoretical predictions based on both bulk matter approximations and density functional theory and Hartree-Fock calculated Ni nanocluster structures (composed of 2-15 atoms for the latter). The calculations suggest that Ni nanoclusters composed of less than 10(2) atoms can be produced repeatably with simple microplasma reactors.