Pt-based nanostructures immobilized on carbon supports have been widely used as electrocatalysts. Their catalytic activity can be improved by support modification including nitrogen doping and coating with nitrogen-containing polymers, where nitrogen atoms possibly interact with surface Pt atoms at a catalyst/support interface. To understand electronic effects of nitrogen-doped and polymer-coated carbon supports on the catalytic activity of Pt-based nanostructured catalysts, we prepared Pt 3 Ni nanoframes (NFs) supported on polybenzimidazole (PBI)-coated and uncoated carbon nanotubes for the oxygen reduction reaction (ORR), and then compared their catalytic activities and electronic properties with those of NFs immobilized on nitrogen-doped and undoped carbon supports. Although both PBI-coating and nitrogen-doping approaches improved the catalytic activity of NFs, ex situ X-ray photoelectron spectroscopy and in situ X-ray absorption spectroscopy revealed that nitrogen doping showed electronic effects on NFs, whereas PBI-coating showed almost no impact on the electronic state of NFs but stabilized Pt(OH) ad species under electrochemical conditions. Our studies demonstrate that difference in microscopic environments of nitrogen atoms at the catalyst/ support interface is highly sensitive to the electronic effects of supports on Pt-based electrocatalysts.

Oxygen reduction reaction (ORR) is a key reaction in future energy generation devices such as polymer electrolyte fuel cells (PEFCs) and metal–air batteries. To drive the ORR in PEFCs, Pt–M alloy nanoparticles (M = Ni) on carbon supports have been used as catalysts. Under electrocatalytic conditions, these electrocatalysts are known to degrade involving particle detachment, agglomeration and metal dissolution.[1] These phenomena can be suppressed by increase metal/support interactions: using heteroatom-doped carbon supports[2] and/or nanostructured Pt–M alloy catalysts.[3] Herein, we report synthesis, activity and durability of Pt–Ni nanowires (NWs) for the ORR in acidic media. The Pt–Ni NWs showed higher ORR electrocatalytic activity than Pt/C. The Pt–Ni NWs showed almost no activity loss even after 50,000 potential cycles in acidic media. Physicochemical measurements including in situ Pt L3-edge X-ray absorption spectroscopy [4] revealed that the Pt surface oxide formation under potential control was suppressed after potential cycles, relative to the initial state. This finding suggests that potential cycles could induce strong metal/support interactions, resulting in the formation of highly durable NW catalysts. References. [1] N. Hodnik, G. Dehm, K.J.J. Mayrhofer, Acc. Chem. Res., 49, 2015–2022 (2016). [2] M. Kato, K. Ogura, S. Nakagawa, S. Tokuda, K. Takahashi, T. Nakamura, I. Yagi, ACS Omega, 3, 9052–9059 (2018). [3] J. Li et al., Science, 354, 1414–1417 (2016). [4] K. Nagasawa et al., J. Am. Chem. Soc., 137, 12856 (2015). Acknowledgements. This work was supported by NEDO.