Modulating paired Ir-O-Ir via electronic perturbations of correlated Ir single atoms to overcome catalytic selectivity

Abstract

Single-atom catalysts have been extensively utilized for electrocatalysis, in which electronic metal-support interactions are typically employed to stabilize single atoms. However, this neglects the metal-metal interactions of adjacent atoms, which are essential for the fine-tuning of selective sites. Herein, the high-loading of Ir single atoms (Ir SAs) (8.9 wt%) were adjacently accommodated into oxygen vacancy-rich Co₃O₄ nanosheets (Ir SAs/Co₃O₄). Electronic perturbations for both Ir single atoms and Co₃O₄ supports were observed under electronic metal-support and metal-metal interactions, thus generating Ir-O-Co/Ir units. Electrons were transferred from Co and Ir to O atoms, inducing the depletion of 3d/5d states in Co/Ir and the occupation of 2p states in O atoms to stabilize the Ir SAs. Moreover, the O atoms of Ir-O-Ir functioned as the main active sites for the electrocatalysis of As(iii), which reduced the energy barrier for the rate-determining step. This was due to the stronger electronic affinities for intermediates from reduction of As(iii), which were completely distinct from other coordinated O atoms of Co₃O₄ or IrO₂. Consequently, the resultant Ir SAs/Co₃O₄ exhibited far more robust electrocatalytic activities than IrO₂/Co₃O₄ and Co₃O₄ in the electrocatalysis of As(iii). Moreover, there was a strong orbital coupling effect between the coordinated O atoms of Ir SAs and the -OH of H₃AsO₃, thus exhibiting superior selectivity for As(iii) in contrast to other common heavy metal cations. This work offers useful insights into the rational design of intriguing SACs with high selectivity and stability for the electrocatalysis and electrochemical analysis of pollutants on an electronic level.