LAUSR

In this study, the electrocatalytic behavior of platinum (Pt) nanoparticles (NPs) in a novel multilayered thin film is investigated for proton exchange membrane fuel cells (PEMFC) applications. The multilayer thin films are assembled by the alternate deposition of branched polyethylenimine (BPEI) and poly(acrylic acid) (PAA) from aqueous solutions through a layer‐by‐layer (LbL) technique. Two extreme assembly pH conditions critically influence the films' physical and morphological characteristics, subsequently affecting their electrochemical behavior. Manipulation of the assembly pH modifies the charge density of the weak polyelectrolytes (BPEI and PAA), leading to variations in physical, structural, and electrochemical properties. The LbL thin films assembled at a pH of 9.5 for BPEI and 4.5 for PAA exhibit significantly greater thickness compared to the same film with all components deposited at pH 4.5. This is attributed to in‐and‐out diffusion of the partially charged polyelectrolytes with coiled polymeric conformation (BPEI at pH 9.5 and PAA at pH 4.5). As‐assembled LbL thin films are used as nanoreactors for the deposition of Pt NPs. The nanoscale control over polymeric conformation and charge density significantly influences electrocatalytic performance. 9.5BPEI/4.5PAA thin films exhibit higher electrocatalytic activity relative to 4.5BPEI/4.5PAA systems. This improved performance in 9.5BPEI/4.5PAA multilayers is ascribed to the fact that more carboxylic acid groups of PAA are coated in an exponentially grown behavior, which provides more active sites available for Pt NPs to be deposited. The multilayer thin films containing uniformly dispersed Pt NPs can be an attractive and advanced hybrid electrode material with great promise for the proton exchange membrane fuel cells.