Grain Boundary Tailors the Local Chemical Environment on Iridium Surface for Alkaline Electrocatalytic Hydrogen Evolution

Abstract

Even though grain boundaries (GBs) have been previously employed to increase the number of active catalytic sites or tune the binding energies of reaction intermediates for promoting electrocatalytic reactions, the effect of GBs on the tailoring of the local chemical environment on the catalyst surface has not been clarified thus far. In this study, a GBs‐enriched iridium (GB‐Ir) was synthesized and examined for the alkaline hydrogen evolution reaction (HER). Operando Raman spectroscopy and density functional theory (DFT) calculations revealed that a local acid‐like environment with H3O+ intermediates was created in the GBs region owing to the electron‐enriched surface Ir atoms at the GBs. The H3O+ intermediates lowered the energy barrier for water dissociation and provided enough hydrogen proton to promote the generation of hydrogen spillover from the sites at the GBs to the sites away from the GBs, thus synergistically enhancing the hydrogen evolution activity. Notably, the GB‐Ir catalyst exhibited a high alkaline HER activity (10 mV @ 10 mA cm‐2, 20 mV dec‐1). We believe that our findings will promote further research on GBs and the surface science of electrochemical reactions.

Ultralow-content Pt nanodots/Ni3Fe nanoparticles: interlayer nanoconfinement synthesis and overall water splitting

“…33 Such a type of interlayer confinement was reported for designing and preparing other nanostructures, such as carbon nanorings, 24 Ir nanodots, 25 and Pt single atoms. 26 The LDH precursor-involved interlayer confinement could thus be universal for developing electrocatalytic water splitting, and also as effective as other types of synthesis strategies, such as metal–organic-framework encapsulation, 34 the grain boundary effect, 35 hierarchical pore confinement, 36 metal–support interaction, 37,38 and lattice strain. 39 In addition, pores were observed on the rGO support (Fig.…”