Two- and Three-Dimensional Au Nanoparticle/CoTMPyP Self-Assembled Nanotructured Materials: Film Structure, Tunable Electrocatalytic Activity, and Plasmonic Properties

Abstract

Two- and three-dimensional Au nanoparticle/[tetrakis(N-methylpyridyl)porphyrinato]cobalt (CoTMPyP) nanostructured materials were prepared by “bottom-up” self-assembly. The electrocatalytic and plasmonic properties of the Au nanoparticle/CoTMPyP self-assembled nanostructured materials (abbreviated as Au/CoTMPyP SANMs) are tunable by controlled self-assembly of the Au nanoparticles and CoTMPyP on indium tin oxide (ITO) electrode. The electrocatalytic activity of the Au/CoTMPyP SANMs can be tuned in two ways. One way is that citrate-stabilized Au nanoparticles are positioned first on ITO surface with tunable number density, and then positively charged CoTMPyP ions are planted selectively on these gold sites. The other way is that Au nanoparticles and CoTMPyP are deposited by virtue of layer-by-layer assembly, which can also tune the amount of the as-deposited electrocatalysts. FE-SEM studies showed that three-dimensional SANMs grow in the lateral expansion mode, and thermal annealing resulted in both surface diffusion of nanoparticles and atomic rearrangement to generate larger gold nanostructures with predominant (111) facets. The annealed SANMs show a strongly enhancing gold surface plasmonic resonance band in comparison with unannealed SANMs. The changes in gold plasmonic properties correlate with annealing-induced structural changes of the SANMs.