Dicyanamide-based Modification of Platinum Surface: Towards Improved Oxygen Reduction Reaction
Ana Herceg a b, Milutin Smiljanić a, Vasko Jovanovski a, Anja Logar a c, Nejc Hodnik a, Primož Jovanovič a
a Department of Materials Chemistry, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia
b Faculty of Chemistry and Chemical Technology, University of Ljubljana, 1001, Ljubljana, Slovenia
c University of Nova Gorica, Vipavska 13, SI-5000 Nova Gorica, Slovenia
Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Spring 2024 Conference (MATSUS24)
#MatInter - Materials and Interfaces for emerging electrocatalytic reactions
Barcelona, Spain, 2024 March 4th - 8th
Organizers: Marta Costa Figueiredo and María Escudero-Escribano
Poster, Ana Herceg, 430
Publication date: 18th December 2023

With the growing awareness of the negative impact of fossil-fuel technologies and significant energy consumption on the environment, it became evident that known technologies must be replaced by »green« ones. In this respect, low temperature proton exchange membrane fuel cells (PEMFCs), which directly convert the chemical energy stored in hydrogen to electricity, seem highly attractive. However, PEMFCs commercialization has so far been rather slow, mainly due to the sluggish oxygen reduction reaction (ORR) on the cathode side which results in high overpotentials and consequently leads to the deterioration of the power conversion efficiency of PEMFCs. The aim of this research is to manipulate with the solid-liquid interface of polycrystalline platinum (Pt-poly). In particular, for the first time, we focus on modification of platinum surface with dicyanamide anions (DCA). Via rotating disc electrode measurements we demonstrate that Pt-DCAads electrode can easily be manipulated towards substantial ORR improvement. Furthermore, to extend the potential range for examining the kinetics of ORR, a modified floating electrode (MFE) configuration, recently introduced by our group, was used. Accordingly, ORR performance was assessed under an elevated mass transport regime enabling us to pursue the reaction closer to PEMFC-relevant current densities. To provide comprehensive understanding of Pt-DCAads interaction we employed several electrochemical reactions as surface probes. Namely, CO stripping (COstripp), hydrogen oxidation reaction (HOR), lead under potential deposition (PbUPD) and N2O reduction reaction. Based on our analysis, DCAads severely blocks Pt surface which inhibits formation of Pt hydroxide/oxide, however still ensures sufficient amount of free active sites. Overall, our approach shows great potential for application in PEMFCs and wider.

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