Electrochemical and coupled XPS studies on Langmuir-Blodgett mixed films of behenic acid and over-grafted platinum nanoparticles: Effect of the behenic acid removal

We report on the behavior of Pt nanoparticles functionalized with 4-mercaptoaniline over-grafted with 2-thiophenecarbonyl chloride. Stable Langmuir-Blodgett (LB) mixed films were built up from these particles with behenic acid (BHA). Such ultra-thin films were transferred onto gold substrates, which allowed the study of their electrochemical response towards Fe[(CN)6]3− and their XPS chemical analysis before and after the BHA removal. After washing, XPS analysis showed that the signals corresponding to the metal core and the capping agent were almost unchanged. Moreover, the layers became more compact, as shown by the Pt/Au intensity ratio decrease, because of the apparent decrease of length escape of electrons coming from gold, evidencing the removal of the fatty acid in the LB film structure. After BHA removal, the resulting electrochemical activity slightly increased. This result, in agreement with XPS analysis, showed the structural rearrangement within the film that facilitated the percolation between the particle domains.