Pt 5d Density of States in Pt3Mg-N-C Catalyst Governed by Ligand Effect
Jiabin Xu1,2, Jiatang Chen3, Yun-Mui Yiu1
1Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada.
Abstract:
In alloy systems, the strain and ligand effects are prevalent, but it is challenging to study the impact of either on the material structure independently. We conducted high-energy-resolution fluorescence detection (HERFD) X-ray absorption spectroscopy (XAS) and resonant X-ray emission spectroscopy (XES)/resonant inelastic X-ray scattering (RIXS) spectroscopy on a Pt3Mg alloy-based carbon material (Pt3Mg-N-C). By introducing a size-comparable atom, the strain effect is minimized, allowing the Pt d-density of states (d-DOS) to be primarily affected by the ligand effect. The experimental results reveal that Pt gains electrons in Pt3Mg-N-C, exhibiting a more symmetric d-band shape and a downshift of the d-band center compared to Pt metal, which is further confirmed by density functional theory (DFT) calculations. The correlation between the Pt d-DOS and oxygen reduction reaction (ORR) activity is also discussed.
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