Enhancing Electrocatalytic Interface of Platinum through Dicyanamide Functionalization

Ana Herceg^a^,^b, Nik Maselj^a^,^b, Vasko Jovanovski^b, Nejc Hodnik^b^,^c, Primož Jovanovič^b

^aFaculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1000 Ljubljana, Slovenia

^bDepartment of Materials Chemistry, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia

^cUniversity of Nova Gorica, Vipavska 13, 5000 Nova Gorica, Slovenia

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Spring 2025 Conference (MATSUSSpring25)

Advances in Electrochemical Energy Storage Systems: Driving Towards a Sustainable Future - #SUSEES

Sevilla, Spain, 2025 March 3rd - 7th

Organizers: Ungyu Paik and Kangli Wang

Oral, Ana Herceg, presentation 176
DOI: https://doi.org/10.29363/nanoge.matsusspring.2025.176
Publication date: 16th December 2024

Present-day technologies contribute significantly to environmental strain through the emission of exhaust gases, underscoring the need for cleaner alternatives. Electrocatalysis offers promising solutions to replace traditional processes in both the manufacturing and energy sectors. More precisely, various electrocatalyst surface modifications have proven effective in improving the Oxygen Reduction Reaction (ORR), a reaction of critical interest in fuel cell technology. Nonetheless, several obstacles impede the commercialization of electrocatalyst surface modifications, one being inadequate quantification of active sites.

Here, we focus on enhancing electrocatalytic interfaces by electrochemically modifying the polycrystalline platinum (Pt-poly) surface to create a more favorable environment for electrocatalytic reactions. We achieve surface modification by electrochemical biasing in the presence of dicyanamide anions (DCA) and then characterize the modified electrode electrochemically. Using rotating disc electrode (RDE) measurements, we analyze surface probe reactions, including N₂O reduction (Potential of Zero Total Charge determination), Oxygen Reduction Reaction (ORR), and Hydrogen Oxidation Reaction (HOR).

Our findings indicate that the newly formed species, transforming platinum into a +2 oxidation state, partially block the platinum surface. Nevertheless, sufficient free active sites remain available for proton, hydrogen, oxygen, and nitrous oxide adsorption and manifest higher catalytic activity towards corresponding reactions. This is likely due to electrostatic interactions, which inhibit water discharge and adsorption of anions. Furthermore, we present a new, non-destructive surface area determination method based on N₂O reduction probing. Overall, the selective nature of this modification holds significant promise for applications in electrocatalytic reactions.

References:

[1] Strmcnik, D.; Escudero-Escribano, M.; Kodama, K. et al. Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide. Nature Chem 2 2010, 880–885.

[2] Zorko, M.; Farinazzo Bergamo Dias Martins, P.; Connell, J.G. et al. Improved Rate for the Oxygen Reduction Reaction in a Sulfuric Acid Electrolyte using a Pt(111) Surface Modified with Melamine. ACS Appl. Mater. Interfaces 13 (2) 2021, 3369-3376.

[3] Wang, H.; Wang, Y.; Li, C. et al. Introduction of Surface Modifiers on the Pt-Based Electrocatalysts to Promote the Oxygen Reduction Reaction Process. Nanomaterials 2023, 13, 1544.

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