p‐Block Bismuth Nanoclusters Sites Activated by Atomically Dispersed Bismuth for Tandem Boosting Electrocatalytic Hydrogen Peroxide Production

Abstract

AbstractConstructing electrocatalysts with p‐block elements is generally considered rather challenging owing to their closed d shells. Here for the first time, we present a p‐block‐element bismuth‐based (Bi‐based) catalyst with the co‐existence of single‐atomic Bi sites coordinated with oxygen (O) and sulfur (S) atoms and Bi nanoclusters (Biclu) (collectively denoted as BiOSSA/Biclu) for the highly selective oxygen reduction reaction (ORR) into hydrogen peroxide (H2O2). As a result, BiOSSA/Biclu gives a high H2O2 selectivity of 95 % in rotating ring‐disk electrode, and a large current density of 36 mA cm−2 at 0.15 V vs. RHE, a considerable H2O2 yield of 11.5 mg cm−2 h−1 with high H2O2 Faraday efficiency of ∼90 % at 0.3 V vs. RHE and a long‐term durability of ∼22 h in H‐cell test. Interestingly, the experimental data on site poisoning and theoretical calculations both revealed that, for BiOSSA/Biclu, the catalytic active sites are on the Bi clusters, which are further activated by the atomically dispersed Bi coordinated with O and S atoms. This work demonstrates a new synergistic tandem strategy for advanced p‐block‐element Bi catalysts featuring atomic‐level catalytic sites, and the great potential of rational material design for constructing highly active electrocatalysts based on p‐block metals.