Simultaneous Generation of H₂O₂ and Formate by Co‐Electrolysis of Water and CO₂ over Bifunctional Zn/SnO₂ Nanodots

Abstract

Abstract Hydrogen peroxide (H 2 O 2 ) and formate are important chemicals used in various chemical manufacturing industries. One promising approach for the simultaneous production of these chemicals is coupling anodic two‐electron water oxidation with cathodic CO 2 reduction in an electrolyzer using nonprecious bifunctional electrocatalysts. Herein, we report an innovative hybrid electrosynthesis strategy using Zn‐doped SnO 2 (Zn/SnO 2 ) nanodots as bifunctional redox electrocatalysts to achieve Faradaic efficiencies of 80.6 % and 92.2 % for H 2 O 2 and formate coproduction, respectively, along with excellent stability for at least 60 h at a current density of ≈150 mA cm −2 . Through a combination of physicochemical characterizations, including operando attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), isotope labeling mass spectrometry (MS)/ 1 H NMR and quasi‐in situ electron paramagnetic resonance (EPR), with density functional theory (DFT) calculations, we discovered that the Zn dopant facilitates the coupling of *OH intermediates to promote H 2 O 2 production and optimizes the adsorption of *OCHO intermediates to accelerate formate formation. Our findings offer new insights into designing more efficient bifunctional electrocatalyst‐based pair‐electrosynthesis system for the coproduction of H 2 O 2 and formate feedstocks.