Molecular Insight of the Critical Role of Ni in Pt-Based Nanocatalysts for Improving the Oxygen Reduction Reaction Probed Using an In Situ SERS Borrowing Strategy

PtNi alloy catalysts have excellent catalytic activity and are considered some of the most promising electrocatalysts capable of replacing pure Pt for the oxygen reduction reaction (ORR). For PtNi alloys, Ni-doping can improve performance by changing the electronic and structural properties of the catalyst surface and its interaction with reaction intermediates. However, to date there is no direct spectral evidence detecting or identifying the effect of Ni on the ORR in PtNi alloy catalysts. Herein, we introduce a surface-enhanced Raman spectroscopic (SERS) borrowing strategy for investigating ORR processes catalyzed by Au@PtNi nanoparticles (NPs). The bond vibration of adsorbed peroxide intermediate species (*OOH) was obtained, and the effect of Ni on the interaction between surface Pt and *OOH was studied by varying the Ni content in the alloy. The frequency of the *OOH spectral band has an obvious red-shift with increasing Ni content. Combined with density functional theory (DFT) calculations, we show that Ni-doping can optimize *OOH surface binding on the Pt surface, achieving more efficient electron transfer, thus improving the ORR rate. Notably, these results evidence the SERS borrowing strategy as an effective technique for in situ observations of catalytic processes.

Automated summary

PtNi alloy catalysts have excellent catalytic activity, with Ni-doping improving performance, but there is no direct spectral evidence detecting the effect of Ni on the ORR. By using a surface-enhanced Raman spectroscopic (SERS) borrowing strategy, the interaction between Ni and *OOH in PtNi catalysts can be studied, showing that Ni can optimize the surface binding of *OOH on Pt for more efficient electron transfer during the ORR.