Accelerated Proton-Coupled Electron Transfer via Engineering Palladium Sub-Nanoclusters for Scalable Electrosynthesis of Hydrogen Peroxide.

Abstract

Electrosynthesis of H2O2 from oxygen reduction reaction via a two-electron pathway is vital as an alternative for the energy-intensive anthraquinone process. However, this process is largely hindered in neutral and alkaline conditions due to sluggish kinetics associated with the transformation of intermediate O2* into OOH* via proton-coupled electron transfer sourced from slow water dissociation. Herein, we developed Pd sub-nanoclusters on the nickel ditelluride nanosheets (Pd SNCs/NiTe2) to enhance the performance of H2O2 electrosynthesis. The newly-developed Pd SNCs/NiTe2 exhibited a H2O2 selectivity of as high as 99% and a positive shift of onset potential up to 0.81 V. Combined theoretical calculations and experimental studies (e.g., X-ray absorption and attenuated total reflectance-Fourier transform infrared spectra measurements) revealed that the Pd sub-nanoclusters supported by NiTe2 nanosheets efficiently reduced the energy barrier of water dissociation to generate more protons, facilitating the proton feeding kinetics. When used in a flow cell, Pd SNCs/NiTe2 cathode efficiently produced H2O2 with a maximum yield rate of 1.75 mmol h-1 cm-2 and current efficiency of 95% at 100 mA cm-2. Further, an accumulated H2O2 concentration of 1.43 mol L-1 was reached after 10 hours of continuous electrolysis, showing the potential for practical H2O2 electrosynthesis.