Nucleation is Second Order: An Apparent Kinetically Effective Nucleus of Two for Ir(0)_n Nanoparticle Formation from [(1,5-COD)Ir~(I)·P_2W_(15)Nb_3O_(62)]~(8-) Plus Hydrogen

摘要

Nucleation initiates phase changes across nature. A fundamentally important, presently unanswered question is if nucleation begins as classical nucleation theory (CNT) postulates, with n equivalents of monomer A forming a "critical nucleus", A_(w) in a thermodynamic (equilibrium) process. Alternatively, is a smaller nucleus formed at a kinetically limited rate? Herein, nucleation kinetics are studied starting with the nanoparticle catalyst precursor, [A] = [(Bu_4N)_5Na_3(1,5-COD)Ir~(I)·P_2W_(15)Nb_3O_(62)], forming soluble/dispersible, B = Ir(0)_(～300) nanoparticles stabilized by the P_2W_(15)Nb_3O_(62)~(9-) polyoxoanion. The resulting sigmoidal kinetic curves are analyzed using the 1997 Finke-Watzky (hereafter FW) two-step mechanism of (ⅰ) slow continuous nucleation (A → B, rate constant k_(1obs)), then (ⅱ) fast autocatalytic surface growth (A + B → 2B, rate constant k_(2obs)). Relatively precise homogeneous nucleation rate constants, k_(1obs), examined as a function of the amount of precatalyst, A, reveal that k_(1obs) has an added dependence on the concentration of the precursor, k_(1obs) = k_(1obs(bimolecular))[A]. This in turn implies that the nucleation step of the FW two-step mechanism actually consists of a second-order homogeneous nucleation step, A + A → 2B (rate constant, k_(1obs(bimol)). The results are significant and of broad interest as an experimental disproof of the applicability of the "critical nucleus" of CNT to nanocluster formation systems such as the Ir(0)_n one studied herein. The results suggest, instead, the experimentally-based concepts of (ⅰ) a kinetically effective nucleus and (ⅱ) the concept of a first-observable cluster, that is, the first particle size detectable by whatever physical methods one is currently employing. The 17 most important findings, associated concepts, and conclusions from this work are provided as a summary.