Scalable neutral H<sub>2</sub>O<sub>2</sub> electrosynthesis by platinum diphosphide nanocrystals by regulating oxygen reduction reaction pathways.

Li, Hui; Wen, Peng; Itanze, Dominique S; Hood, Zachary D; Adhikari, Shiba; Lu, Chang; Ma, Xiao; Dun, Chaochao et al. · Nat Commun · 2020

basic_science · Level V

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Abstract

Despite progress in small scale electrocatalytic production of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) using a rotating ring-disk electrode, further work is needed to develop a non-toxic, selective, and stable O<sub>2</sub>-to-H<sub>2</sub>O<sub>2</sub> electrocatalyst for realizing continuous on-site production of neutral hydrogen peroxide. We report ultrasmall and monodisperse colloidal PtP<sub>2</sub> nanocrystals that achieve H<sub>2</sub>O<sub>2</sub> production at near zero-overpotential with near unity H<sub>2</sub>O<sub>2</sub> selectivity at 0.27 V vs. RHE. Density functional theory calculations indicate that P promotes hydrogenation of OOH* to H<sub>2</sub>O<sub>2</sub> by weakening the Pt-OOH* bond and suppressing the dissociative OOH* to O* pathway. Atomic layer deposition of Al<sub>2</sub>O<sub>3</sub> prevents NC aggregation and enables application in a polymer electrolyte membrane fuel cell (PEMFC) with a maximum r(H<sub>2</sub>O<sub>2</sub>) of 2.26 mmol h<sup>-1</sup> cm<sup>-2</sup> and a current efficiency of 78.8% even at a high current density of 150 mA cm<sup>-2</sup>. Catalyst stability enables an accumulated neutral H<sub>2</sub>O<sub>2</sub> concentration in 600 mL of 3.0 wt% (pH = 6.6).