Electrodeposited PtNi nanoparticles towards oxygen reduction reaction:A study on nucleation and growth mechanism

In this work,highly monodispersed Pt-Ni alloy nanoparticles were directly deposited on carbon substrate through a facile electrodeposition strategy in the solvent system of N,N-dimethylformamide(DMF).A series of carbon supported Pt-Ni alloy electrocatalysts were synthesized under different applied electrode potentials.Among all as-obtained samples,the Pt-Ni/C electrocatalyst deposited at-1.73 V exhibits the optimal specific activity up to 1.850 mA cm^(-2)at 0.9 V vs.RHE,which is 6.85 times higher than that of the commercial Pt/C.Comprehensive physiochemical characterizations and computational evaluations via density functional theory were conducted to unveil the nucleation and growth mechanism of PtNi alloy formation.Compared to the aqueous solution,DMF solvent molecule must not be neglected in avoiding particle agglomeration and synthesis of monodispersed nanoparticles.During the alloy co-deposition process,Ni sites produced through the reduction of Ni(Ⅱ)precursor not only facilitates Pt-Ni alloy crystal nucleation but also in favor of further Pt reduction on the Ni-inserted Pt surface.As for the deposition potential,it adjusts the final particle size.This work provides a hopeful extended Pt-based catalyst layer production strategy for proton exchange membrane fuel cells and a new idea for the nucleation and growth mechanism exploration for electrodeposited Pt alloy.

Self-Decoration of PtNi Alloy Nanoparticles on Multiwalled Carbon Nanotubes for Highly Efficient Methanol Electro-Oxidation

A simple one-pot method was developed to prepare Pt Ni alloy nanoparticles,which can be self-decorated on multiwalled carbon nanotubes in [BMIm][BF4] ionic liquid.The nanohybrids are targeting stable nanocatalysts for fuel cell applications.The sizes of the supported Pt Ni nanoparticles are uniform and as small as 1–2 nm.Pt-to-Ni ratio was controllable by simply selecting a Pt Ni alloy target.The alloy nanoparticles with Pt-to-Ni ratio of 1:1 show high catalytic activity and stability for methanol electro-oxidation.The performance is much higher compared with those of both Pt-only nanoparticles and commercial Pt/C catalyst.The electronic structure characterization on the Pt Ni nanoparticles demonstrates that the electrons are transferred from Ni to Pt,which can suppress the CO poisoning effect.

Calibrating SECCM measurements by means of a nanoelectrode ruler.The intrinsic oxygen reduction activity of PtNi catalyst nanoparticles

Scanning electrochemical cell microscopy(SECCM)is increasingly applied to determine the intrinsic catalytic activity of single electrocatalyst particle.This is especially feasible if the catalyst nanoparticles are large enough that they can be found and counted in post-SECCM scanning electron microscopy images.Evidently,this becomes impossible for very small nanoparticles and hence,a catalytic current measured in one landing zone of the SECCM droplet cannot be correlated to the exact number of catalyst particles.We show,that by introducing a ruler method employing a carbon nanoelectrode decorated with a countable number of the same catalyst particles from which the catalytic activity can be determined,the activity determined using SECCM from many spots can be converted in the intrinsic catalytic activity of a certain number of catalyst nanoparticles.