Electronic Ensemble Effects of Organic/Inorganic Hybrid Surface on PtCo Nanoparticles for Oxygen Reduction Reactions
- Electronic Ensemble Effects of Organic/Inorganic Hybrid Surface on PtCo Nanoparticles for Oxygen Reduction Reactions
- 정남기; Satadeep Bhattacharjee; Sanjeev Gautam; 박희영; 류재윤; 정영훈; 이상영; 장인준; 장종현; 박세흠; 정동영; 성영은; 채근화; Umesh V Waghmare; 이승철; 유성종
- 연료전지; 합금촉매; 산소환원반응; PtCo; PNIPAM
- Issue Date
- NPG asia materials
- VOL 8, 237
- In Pt-transition metal (TM) alloy catalysts, the electron transfer from the TM to Pt is retarded owing to the inevitable oxidation of the TM surface by oxygen. In addition, acidic electrolytes such as those employed in fuel cells accelerate the dissolution of the surface TM oxide, which leads to catalyst degradation. Herein, we propose a novel synthesis strategy that selectively modifies the electronic structure of surface Co atoms with N-containing polymers, resulting in highly active and durable PtCo nanoparticle catalysts useful for the oxygen reduction reaction (ORR). The polymer, which is functionalized on carbon black, selectively interacts with the Co precursor, resulting in Co–N bond formation on the PtCo nanoparticle surface. Electron transfer from Co to Pt in the PtCo nanoparticles modified by the polymer is enhanced by the increase in the difference in electronegativity between Pt and Co compared with that in bare PtCo nanoparticles with the TM surface oxides. In addition, the dissolution of Co and Pt is prevented by the selective passivation of surface Co atoms and the decrease in the O-binding energy of surface Pt atoms. As a result, the catalytic activity and durability of PtCo nanoparticles for the ORR are significantly improved by the electronic ensemble effects. The proposed organic/inorganic hybrid concept will provide new insights into the tuning of nanomaterials consisting of heterogeneous metallic elements for various electrochemical and chemical applications.
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